Radja Nainggolan's first European goal for his new club and a cool Mauro Icardi finish on the hour gave the Nerazurri their second comeback victory of the campaign, having dramatically beaten Tottenham 2-1 a fortnight ago.
No late fireworks were required on this occasion, although Inter were still made to work for their fifth straight victory in all competitions after falling behind to a Pablo Rosario stunner.
Nainggolan restored parity on the stroke of half-time before Icardi, one of the heroes of the Spurs success, took Luciano Spalletti's side level on points with leaders Barca after two encouraging outings.
An entertaining first half promised goals from the outset and Rosario emphatically delivered in the 27th minute, whipping a sensational effort from right to left and past a flat-footed Samir Handanovic.
Two chances for Icardi suggested a response was forthcoming, although Inter received a let-off when the onrushing Handanovic escaped with a yellow card for handling the ball outside the area.
Mark van Bommel felt the goalkeeper's impeding of Steven Bergwijn deserved red and his mood was not helped a minute before the break, Nainggolan rifling in the equaliser from the edge of the box.
Gaston Pereiro curled a shot against the upright soon after the restart but, for all PSV's promise, they struggled to ever get to grips with Icardi.
The 25-year-old's 60th-minute winner owed as much to Jeroen Zoet's error as individual brilliance, the goalkeeper colliding with Daniel Schwaab and leaving Icardi to roll the ball into an empty net.
Handanovic was required to make one final save from an inventive Donyell Malen overhead kick 10 minutes from the end that maintained his team's perfect start in Group B.
What it means: Inter on course
This was no easy for assignment for Inter, a lesson they quickly learned during a testing first half hour.
However, just as it had been at San Siro two weeks earlier, plenty of character was on display in a fightback that means they are now in pole position to advance alongside Barca.
Icardi on form
Where would Inter be without their inspirational skipper?
The Argentina star was not always entirely clinical at Philips Stadion, but his hold-up play and all-round threat made him a worthy provider of the winner.
Zoet causes PSV collapse
One smart save from a first-half Icardi header was not enough to paper over a poor Zoet performance.
The PSV keeper was at fault for both Inter goals as his handling error led to Nainggolan's equaliser, while a wild attempt at beating Icardi to the second left Schwaab with no chance of rescuing the situation.
Key Opta stats
- Inter have never lost to Dutch opposition in the Champions League in nine matches (W7 D2), the most they have faced teams from a single nation without defeat in the competition.
- Inter manager Luciano Spaletti has recorded consecutive wins in the competition for the first time since December 2008 (a run of three while at Roma).
- PSV are winless in their last 10 games in the Champions League (D4 L6); their longest such run in competition history.
- Mauro Icardi has scored 14 goals in his last 18 appearances for Inter in all competitions – scoring in three of his last four games.
- PSV’s Pablo Rosario became the 100th Dutch player to score a goal in the Champions League.