As the Gunners finished in the automatic qualification places in the League Phase, this will be their first European game since January 29.
That allowed them to sit out of the play-off round that saw Manchester City knocked out, before they were then drawn against PSV.
The Dutch side impressively eliminated Juventus to reach the knockout stages and now they will take on Mikel Arteta's side for a place in the quarter-finals.
Kick-off at the Philips Stadion is scheduled for 8pm.
Live commentary: talkSPORT website stream HERE, via the app HERE/ Live stream: TNT Sports
PSV XI: Benítez, Malacia, Boscagli, Flamingo, Ledezma, Saibari, Schouten, Lang, Til, Perisic, De Jong.
Subs: Drommel, Schiks, Karsdorp, Obispo, Bakayoko, Driouech, Veerman, Babadi, Land, Nagalo
Arsenal XI: Raya; Timber, Saliba, Gabriel, Lewis-Skelly; Odegaard, Partey, Rice; Nwaneri, Merino, Trossard.
Subs: Neto, Setford, White, Kiwior, Zinchenko, Tierney, Calafiori, Jorginho, Sterling, Kabia, Butler-Oyedeji.
Follow minute-by-minute updates of PSV vs Arsenal in our dedicated live blog here…
a minute agoBy Joe Brophy
GOAL!! PSV 0-1 Arsenal Jurrien Timber
THAT'S HOW FAST A MATCH CAN CHANGE!
Timber on his return to the Netherlands heads home Rice's cross from close range to give the visitors a priceless lead.
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3 minutes agoBy Joe Brophy
PSV 0-0 Arsenal CROSSBAR
16' - DOUBLE LET OFF FOR THE GUNNERS!!
How have PSV not taken the lead?! Saibari smashes the frame of the goal from yards out with their first clear-cut attack.
Raya does poorly with a Perisic cut back from the byline as under no pressure he parries it into a dangerous area.
Saibari arriving looks to have a tap-in but under pressure from Gabriel gets underneath it and smashes the crossbar.
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7 minutes agoBy Joe Brophy
PSV 0-0 Arsenal NO GOAL
12' - RICE HAS THE BALL IN THE NET BUT NO GOAL!
The England midfielder is stopped in his tracks before he can start to wheel away by the offside flag.
He'd just gone early with his run beyond Man United loanee Malacia but his finish inside the far bottom corner was a well-taken one.
It continues an early theme for Arteta's men - 52% of Arsenal's attacks in the opening 12 minutes of this game have down their left-hand side.
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9 minutes agoBy Joe Brophy
PSV 0-0 Arsenal NO PENALTY
9' - ODEGAARD GOES DOWN IN THE BOX!!
The Gunners captain is adamant that he's been clipped on his heels as he breaks into the area and prepares to shoot.
The Norwegian pulls back his leg before he tangles with the recovering Saibari. His appeals are waved away.
VAR has a look but refuses to intervene - no penalty!
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10 minutes agoBy Joe Brophy
PSV 0-0 Arsenal
7' - Bright from Nwaneri!
The Arsenal teenager stands up a delicate cross towards the back post which has PSV defenders backpedalling.
However, Arsenal again have no striker following in to head home.
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13 minutes agoBy Joe Brophy
PSV 0-0 Arsenal
5' - BIG LET-OFF FOR THE GUNNERS!
A powerful header in the middle of the park from Saibari somehow cuts through the Arsenal midfield like a knife through butter.
It breaks favourably for Lang who has Perisic out wide to release in a two-on-two break but his pass is woefully underhit.
It allows Saliba valuable time to recover and nip in ahead of the former Tottenham winger to clear for the visitors.
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16 minutes agoBy Joe Brophy
PSV 0-0 Arsenal
3' - A half-opening for the Gunners as Lewis-Skelly almost opens up the PSV defence by slotting through for Odegaard.
However, the pass is slightly overhit and trickles out of reach of the Arsenal captain - positive start though fo the visitors!
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19 minutes agoBy Joe Brophy
PSV 0-0 Arsenal KICK-OFF!
1' - WE ARE UNDERWAY!
Arsenal are unbeaten in their five home matches in European competitions against PSV (W3 D2), the most home games they've played against an opponent in European competition without ever losing.
Away from home, however, they're winless in their last four against the Dutch side (D2 L2), with their only win away to them coming in September 2002 (4-0 in the UEFA Champions League).
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22 minutes agoBy Joe Brophy
PSV vs Arsenal: talkSPORT coverage
talkSPORT will have live coverage of all the action and commentary will come from Sam Matterface and Scott Minto.
To tune in to talkSPORT or talkSPORT 2 through the website, click HERE for the live stream.
You can also listen via the talkSPORT app, on DAB digital radio, through your smart speaker and on 1089 or 1053 AM.
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28 minutes agoBy Joe Brophy
Why Lucas Perez cannot play tonight
Lucas Perez will miss the chance to face former club Arsenal in the Champions League despite signing for PSV Eindhoven.
The experienced Spanish striker has joined the Dutch club until the end of the season after having his contract terminated at Deportivo La Coruna for personal reasons.
Since signing for PSV, the forward has made two appearances for the club, but he won't add to that in the Champions League.
Instead, he will have to watch from the sidelines - find out why below...
Why Lucas Perez cannot face former club Arsenal in Champions League after PSV move
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43 minutes agoBy Joe Brophy
Arteta: Arsenal have to step up standards
Arsenal manager Mikel Arteta to Amazon Prime Sport: "We clearly have to adapt. We are clearly missing a lot of players up front. But we have other qualities. We have to be different, we need to be adaptable because we know after 60 or 70 minutes, we may have to change it as well.
"We have only been consistent in the group stages, only conceding three goals. And it's vital. When you keep clean sheets, you have every chance to win games.
"There's a lot of history at PSV. A lot of great players played here. And it's the Champions League. You can feel it on the players that there's something else.
"You are in or you are out. You play two games, you know what you have to do. You have to step up your standards because it's something else."
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45 minutes agoBy Joe Brophy
Gunner be up for the cup
Arsenal have been ahead on the scoreboard for 57% of their minutes played in the UEFA Champions League this season; the highest percentage of any side.
Meanwhile, Mikel Arteta's side have trailed for just 65 of their 770 minutes of match time in the competition this term (8%).
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55 minutes agoBy Joe Brophy
Arteta previews the match
Arsenal manager Arteta has called on fans to keep believing despite two damaging results in a row leading up to this game.
He said: "Stay with them [the squad]. They're an absolute joy to work with. They feel stretched, they feel like they are giving everything they possibly can.
"The way they behave and the way they want it. So be with them, because that's what we all need right now."
On taking on PSV, the Gunners boss added: "We are very much looking forward to it. It's a competition we've performed tremendously well in this season.
"We fought hard to get into this position. And now, as we enter the knockout stages, the building starts now."
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Today, 19:20By Joe Brophy
PSV vs Arsenal: Match stats
Arsenal have only lost one of their last 14 games against Dutch sides in the UEFA Champions League (0-1 v PSV in 2007), although more than half of those matches have ended level (W5 D8 L1).
Arsenal have faced Peter Bosz's PSV side twice previously in the UEFA Champions League, beating them 4-0 at the Emirates and drawing 1-1 away in the 2023-24 group stage.
Arsenal have won each of their last four games in the UEFA Champions League, scoring 13 goals and only conceding twice in the process. The last time they had a five-game win streak in a single edition was in 2005-06 (5), which was when they registered their best ever finish in the competition (runners-up).
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Today, 19:14By Joe Brophy
Thousand Myles
Through Ethan Nwaneri (17y 348d) and Myles Lewis-Skelly (18y 159d) Arsenal are starting a UEFA Champions League game with two teenagers for the first time since September 2014 vs Galatasaray (Héctor Bellerín & Calum Chambers).
The last time the Gunners did so in the knockout rounds of the competition was even further back in March 2007.
Ironically, that was when they met PSV in the last 16 and Cesc Fàbregas started alongside Denilson.
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Today, 19:04By Joe Brophy
Nwan and only!
Ethan Nwaneri is primed to make some history from the second this match kicks-off after being named in the starting XI!
The 17-year-old has stepped up to cover for the injured Bukayo Saka and Gabriel Martinelli, playing regularly on the wing for Arsenal this season.
And he will now become the second-youngest Gunners player ever to appear in a knockout stage game in the Champions League.
He is following in the footsteps of Cesc Fabregas who also did so aged 17.
On top of that, Nwaneri will also emulate Jude Bellingham and Phil Foden in becoming the third English player to start in a Champions League knockout game while under 18.
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Today, 18:48By Joe Brophy
PSV vs Arsenal team news
PSV's Luuk de Jong leads the line tonight for what is his 50th UEFA Champions League appearance.
He is just the fifth Dutch striker to reach this milestone in the competition, after Ruud van Nistelrooij (73), Patrick Kluivert (71), Roy Makaay (61) and Robin van Persie (59).
Meanwhile, Ethan Nwaneri will become the second-youngest Arsenal player to appear in a UEFA Champions League knockout stage game (17y 348d today), after Cesc Fàbregas v Bayern Munich in March 2005 (17y 309d).
He will also become just the third English player to start in a knockout stage game in the competition while under 18, after Jude Bellingham and Phil Foden.