The Gunners scored seven goals in Europe's premier competition for just the second time in their history - and in doing so, became the first away team ever to do so during the knockout stages.
The remarkable goal haul came after Mikel Arteta's side had not scored in their previous two Premier League outings against West Ham and Nottingham Forest.
Arsenal were 3-0 up after just 31 minutes following goals from Jurrien Timber, Ethan Nwaneri and Mikel Merino.
Noa Lang pulled a goal back from the penalty spot before the break, but two goals within three minutes of the restart had the hosts in complete control.
Martin Odegaard brought up his second of the match and Arsenal's sixth in the 73rd minute, before substitute Riccardo Calafiori sealed the stunning rout 12 minutes later.
3 minutes agoBy Joe Brophy
Jur kidding
Arsenal defender Jurrien Timber speaking to Amazon Prime: "Massive performance from the team.
"I'm proud of the guys, we have shown today in the Champions League again that we are capable of a lot and put ourselves in a good position for next week.
"Let's finish it, then we'll see."
On his goal: "Amazing cross, good header. Nice to open the score. I had to win here, rivals of Ajax so I had to win here."
On trip to Madrid in quarter-final: "We put ourselves in a good position for next week. We get it done there and we'll see."
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6 minutes agoBy Joe Brophy
Ethan you're the Nwan
More from Declan Rice on Ethan Nwaneri: "Top. He's 17-years-old and he's on the biggest stage. It's crazy!
We see him every day. All of the lads have taken him under our wing, the same with Myles. You should see them train, they have no fear and the way they want to perform.
"Even if [Bukayo] Saka was here Ethan would be still getting minutes in and around the team because he's that good and works so hard in training. Same with Myles despite having to come off for the yellow card tonight, we have two youngsters and plenty more are coming through."
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11 minutes agoBy Joe Brophy
Rice: We've been playing like this all season!
Arsenal midfielder Declan Rice to Amazon Prime Sport: "We were fluid, we had enthusiasm. We had the drive and hunger, it's the knockout rounds of the Champions League.
"But we have playing like this all season. We spoke about a narrative but we players feel like we've been doing well. Sometimes we score five or six, sometimes we score two or three, sometimes we can lose by one.
"That's where we need to keep pushing as a team with the mentality. Tonight we did that.
"When they came back to make it 3-1, we could have sat back. But we pushed on and you saw that with the goals we scored in the second half. A massive performance.
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18 minutes agoBy Joe Brophy
PSV 1-7 Arsenal REACTION
Arsenal recorded their biggest Champions League knockout win in history as they eased to a 7-1 win away at PSV on Tuesday night.
The Gunners scored seven goals in Europe's premier competition for just the second time in their history as Mikel Arteta's men all-but secured their place in the quarter-finals.
Having not scored in their previous outings against West Ham and Nottingham Forest, there was fear from fans that their season was beginning to unravel.
While the Premier League title is seemingly out of reach with Liverpool 13 points clear, Arsenal showed at the Philips Stadion they mean business in Europe.
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25 minutes agoBy Joe Brophy
PSV 1-7 Arsenal FULL-TIME
The whistle is sounded fairly sharpish to avoid any further humiliation for the home side!
Arsenal have utterly bamboozled and picked apart PSV tonight to guarantee their place against one of the Madrid clubs in the quarters.
The Gunners are the first side in Champions League history to score 7 goals away from home in the knockout stages.
All that's left is the formality of a second leg with no pressure but one of Real or Atletico Madrid will be next up...
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27 minutes agoBy Joe Brophy
PSV 1- 7 Arsenal
88' - Malacia lunges into White in frustration and picks up a late booking.
Not going well for Man United or their loanees at the moment - Rashford aside, with Aston Villa winning earlier this evening...
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32 minutes agoBy Joe Brophy
GOAL!! PSV 1- 7 Arsenal Riccardo Calafiori
85' - SEVEN HEAVEN FOR THE GUNNERS!!!!!!!!
The left-back scoring from the right-wing just about sums up the type of night Arsenal have enjoyed tonight.
Calafiori is delightfully picked out by Odegaard's threaded-through ball but then shows why he was indeed a striker growing up.
He arrives onto the pass and his first-time shot on the swivel beats Benitez and sneaks inside the far post.
Arsenal are the first side in Champions League history to score 7 goals away from home in the knockout stages.
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34 minutes agoBy Joe Brophy
PSV 1-6 Arsenal
83' - Obispo and Veerman are on for Boscagli and Saibara.
Rice, who has not been afforded a rest by Arteta's changes, proves why with a lung-busting run down the pitch to win his side a corner.
Even at 6-1 up!
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35 minutes agoBy Joe Brophy
PSV 1-6 Arsenal
80' - Zinchenko so close to making it seven!
Tierney serves up a timely reminder of his quality by dinking a lovely ball over the top of the PSV defence and Zinchenko volleys at goal.
Benitez reacts well to tip it around the post.
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40 minutes agoBy Joe Brophy
PSV 1-6 Arsenal
77' - Another double switch for Arsenal - White and Tierney are on for Merino and Timber.
Trossard moves up front while Tierney is at left wing.
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44 minutes agoBy Joe Brophy
GOAL!! PSV 1-6 Arsenal Martin Odegaard
73' - IT IS SIX - COMPLETE AND UTTER ANNIHILATION!
PSV fans have seen enough and are leaving in their droves but where has this killer instinct been in front of goal from the Gunners?!
Merino turns well and tees up captain Odegaard in the right half space to burst forwards and drive into the middle.
The Norwegian drops a shoulder to open up the angle for a shot and he fires straight at Benitez who flaps it into his own net.
Odegaard has scored as many non-penalty goals this evening as he managed in his previous 33 appearances in all competitions.
This is the first time Arsenal have scored 6 away from home in Europe since November 1993, beating Standard Liege 7-0 in the Cup Winners' Cup en route to winning the trophy
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47 minutes agoBy Joe Brophy
PSV 1-5 Arsenal NO GOAL
71' - Trossard rounds the goalkeeper to slot into an empty net before seeing the offside flag raised - it stays at five!
The break in play affords Arteta the opportunity to make another double change - Nwaneri and Partey depart, and Timber stays on.
Sterling and Zinchenko come on for the final third of the match!
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48 minutes agoBy Joe Brophy
PSV 1-5 Arsenal
69' - The game has understandably dropped in level following the Gunners' fast-start to the second half.
Timber is booked for taking too long to take a free-kick and instantly Zinchenko is getting stripped and ready to come on.
Arteta is taking zero chances with any suspensions today!
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52 minutes agoBy Joe Brophy
PSV 1-5 Arsenal
65' - Another double change for the home side as De Jong shakes his head when seeing his number called.
Not been his night tonight - The Dutchman departs alongside Ledezma for Bakayoko and Karsdorp.
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57 minutes agoBy Joe Brophy
PSV 1-5 Arsenal
61' - GABRIEL GOES CLOSE!
Arsenal's set-piece man is predictably the intended target from the corner and the Brazilian rises highest to attack the delivery.
But his back post header is sent into the ground before bouncing behind - there's a scream of frustration from Gabriel afterwards!
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58 minutes agoBy Joe Brophy
PSV 1-5 Arsenal
59' - Nwaneri has another pop at goal from the edge of the area but it's headed behind for a corner.
More bright work from Odegaard whose powerful run through the middle engineered the opportunity.
The Arsenal captain looks reinvigorated by ending his goal drought.
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Today, 21:16By Joe Brophy
PSV 1-5 Arsenal
55' - SO CLOSE to a special Nwaneri goal!
The Arsenal teenager is understandably playing full of confidence and he goes alone with a mazy run through the middle.
He opts against looking to feed Trossard and drops a shoulder to ghost past several defenders before firing straight at Benitez.
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Today, 21:15By Joe Brophy
PSV 1-5 Arsenal
PSV conceded 5+ goals in a European competition game for the first time since September 1994 (5-4 v Bayer Leverkusen in the UEFA Cup) and for the first time ever at home in European football.
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Today, 21:09By Joe Brophy
GOAL!! PSV 1-5 Arsenal Leandro Trossard
THIS IS BECOMING A ROUT!!
Trossard gets in on the action and boos are ringing out around the stands - this is becoming humiliating.
Trossard combines with substitute Calafiori down the left before breaking into the box and dinking Benitez from a tight angle.
99 seconds between the two goals...
This is the first time Arsenal have ever scored more than three goals in an away UEFA Champions League knockout stage game.
It is also the earliest an away side has ever scored five goals in an away UEFA Champions League game (48th minute).
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Today, 21:08By Joe Brophy
GOAL!! PSV 1-4 Arsenal Martin Odegaard
JUST A MINUTE AFTER THE RESTART ODEGAARD POUNCES!!
Arsenal's three-goal advantage is restored and silence has emanated around the stadium as any hopes of a cutback is snuffed out.
Nwaneri's tireless work is at the heart of it as he stands up Man United loanee Malacia and leaves him for dead.
He breezes to the byline and fires over a low cross that is spilled poorly by Benítez into a dangerous area.
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