Mikel Arteta's men punched their ticket to Europe's elite competition via a second-placed finish in the 2022-23 Premier League, while their Dutch counterparts avenged last summer's playoff loss to Rangers.
Match preview
The last time that the bright lights of the Emirates Stadium shone down on a Champions League match, Arsene Wenger's Arsenal crop of 2016-17 sought to reverse a 5-1 last-16 deficit against familiar foes Bayern Munich, only to suffer an identical humiliation in front of their own fans.
What followed that 10-2 embarrassment was Wenger's belated departure, the ill-fated Unai Emery era and a rare season without any form of European football, but Arsenal will finally dine at Europe's top table once again in the coming weeks, although qualification was only a consolation prize after their title charge crashed and burned in the latter stages of last term.
Nevertheless, the Gunners - who have never hoisted the Champions League trophy aloft - have managed to avoid one of the more intimidating draws on offer in the group stage, as two struggling sides in Lens and Europa League holders Sevilla will also be vying for the top two places in Group B.
Arsenal have not dazzled on the attacking front so far this term, but Leandro Trossard provided the necessary spark to secure a 1-0 win over Everton at Goodison Park, where Arsenal were also without a win since Wenger was at the helm in 2017-18, and they remain unbeaten in all competitions this season.
However, home clean sheets continue to elude the Gunners, whose only Emirates shut-out in their last 11 games came on the final day of last season against Wolverhampton Wanderers, and an imminent North London derby may also be playing on the minds of Arteta's troops.
On account of their defeat to Rangers at the final qualifying hurdle last year, PSV were condemned to Europa League group-stage football, where they were bested 1-0 by Arsenal at the Emirates before putting the Gunners to the sword 2-0 at Philips Stadion a week later.
The Rood-witten's hopes of Europa League glory were quickly dashed by eventual winners Sevilla in the playoff round, but lightning would not strike twice for the Gers this time around, as after comfortably dispatching Sturm Graz in qualifying, Peter Bosz's men swept the Scottish giants aside 7-3 on aggregate.
A 5-1 home thumping in Eindhoven rubber-stamped PSV's return to the Champions League group stages, where they have not been present since the 2018-19 season, and the Farmers still have just the one European Cup to their name from the 1987-88 campaign, where they bested Benfica on penalties in the final.
Since that inaugural triumph 35 years ago, a semi-final exit in 2005 has represented PSV's deepest run, but Bosz's men have found their best shooting boots this term and crushed NEC 4-0 in the weekend's Eredivisie affair, cementing their place at the top of the table in the process.
Now unbeaten in a staggering 26 competitive matches, PSV have also found the back of the net at least twice in each of their last eight contests and beat Arsenal 2-1 on aggregate in the last 16 of the 2006-07 Champions League, but they have only ever scored once away from home against the Gunners and must harness their recent goalscoring exploits to spoil the North London party.
Arsenal form (all competitions):
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W
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D
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W
PSV Eindhoven Champions League form:
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D
W
PSV Eindhoven form (all competitions):
W
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D
W
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Team News
Already working without a trio of known absentees in Thomas Partey (groin), Jurrien Timber and Mohamed Elneny (both knee), Arsenal suffered another untimely blow at the weekend, as Gabriel Martinelli tweaked his hamstring while running through to score a goal which was ultimately disallowed.
The Brazilian's issue will be assessed ahead of Wednesday, but Trossard will expect to take his place in the XI owing to his match-winning cameo at Goodison Park, where David Raya was also introduced in between the sticks in place of Aaron Ramsdale, but Arteta has suggested that he will continue to chop and change his goalkeepers as the season progresses.
It is anybody's guess as to who will act as the last line of defence for the Gunners this week, and Arteta may also be tempted to bring Gabriel Jesus into the fray for his first start of the season, as Eddie Nketiah struggled to get into the game at Everton.
In strikingly similar fashion, PSV were also dealt a concern with one of their key attackers at the weekend, as winger Noa Lang was forced off the field 11 minutes into the second half against NEC and has emerged as a doubt for the trip to England.
However, Bosz has a ready-made replacement in Hirving Lozano, who made his second debut for PSV off the bench at the weekend, but defensive trio Armando Obispo, Fredrik Oppegard and Mauro Junior are all confined to the treatment room.
PSV addressed their ongoing rearguard concerns by striking a loan deal for Southampton's Armel Bella-Kotchap, who should be named in the first XI at the Emirates, while captain Luuk de Jong has already come up with 14 goal contributions in just nine games this term - nine of his own and five assists.
Arsenal possible starting lineup:
Ramsdale; White, Saliba, Gabriel, Zinchenko; Odegaard, Rice, Vieira; Saka, Jesus, Trossard
PSV Eindhoven possible starting lineup:
Benitez; Teze, Ramalho, Bella-Kotchap, Dest; Schouten, Veerman; Bakayoko, Saibari, Lozano; De Jong
We say: Arsenal 2-1 PSV Eindhoven
PSV may have dominated Arsenal during their most recent showdown 11 months ago, but with no Xavi Simons or Ibrahim Sangare running the show, even the most goal-happy of Rood-witten crops should have their work cut out in North London given the increase in opposition calibre.