- Bukayo Saka (8')
- Leandro Trossard (20')
- Gabriel Jesus (38')
- Martin Ødegaard (70')
Six years after their last appearance among Europe's elite, goals by Bukayo Saka, Leandro Trossard and Gabriel Jesus before half-time paved the way for an easy victory, with captain Martin Ødegaard also on target in the second half.
Saka, one of several Arsenal players making their debuts in the competition, struck from close range after eight minutes and Trossard's low shot made it 2-0 12 minutes later before Jesus hammered Arsenal's third to effectively wrap up the points.
The last time Arsenal played in the Champions League they suffered a chastening 10-2 aggregate drubbing at the hands of Bayern Munich, since when their perennial place amongst the Premier League's top-four became a fading memory.
Runners-up spot to Manchester City last season sent them back to the top table and Dutch side PSV proved the perfect opponents on a rain-drenched night in north London.
"It was a beautiful night," Arsenal manager Mikel Arteta told reporters. "In both boxes today we were exceptional and that was the difference.
"I was really excited before the game. Our journey started last year and we earned the right to be in this competition."
Arsenal have had to grind out wins this season in the Premier League with teams defending deep to negate their attacking strengths.
But Dutch league leaders PSV were wide open, allowing Arsenal to do more or less what they pleased.
After that it was one-way traffic.
Arsenal's opener arrived as Saka linked with Ødegaard and when the Norwegian's shot was only parried by Walter Benítez, Saka was alert enough to guide home from close range.
PSV were architects of their own downfall for Arsenal's second, giving the ball away during a foray forward, and a lightning counter-attack ended with Saka squaring for Trossard to fizz a low shot across the wet turf and into the corner.
Trossard then turned provider to set up Jesus who took a silky touch before smashing a shot into the net.
With a north London derby against Tottenham Hotspur on Sunday, Arsenal manager Mikel Arteta had the luxury of making substitutions throughout the second half with Saka, Jesus and Declan Rice all getting an early breather.
But Arsenal were still far too slick for their opponents and captain Ødegaard drilled in a clinical fourth after 70 minutes to complete a thoroughly satisfying night.
Tougher tests will come but Ødegaard believes Arsenal can have a deep run.
"You saw the motivation and energy right from the start. To be back in this competition is huge for this club," he said. "We are in this competition to compete and fight to go all the way."
- Felix Zwayer