Barca crushed PSV back in September during the first matchday, and Lionel Messi got a hat trick in that one.
Harry Winks hit the frame of the goal as Spurs pushed for the win they needed and substitute Christian Eriksen duly provided it 10 minutes from time when he fired home from close range.
In Group A Atletico and Dortmund are through but have yet to settle who is first and who is second.
The finish sees the Argentine superstar reclaim the record for most Champions League goals for one club, surpassing the mark of 105 set by Ronaldo during his time at Real Madrid. "In the first half, we lost a lot of easy balls".
PSV hasn't won in its last 12 Champions League outings. Luuk de Jong's 83rd-minute header came too late.
PSV are off to a ideal start in the Eredivisie and are gaining consideration as one of the great Eredivisie teams in history. De Jong is hard to defend against and we suffered.
It led to a nervy end to the match for Barca, and Denzel Dumfries had a strong injury-time penalty shout turned down after Clement Lenglet appeared to catch him in the box with a clumsy challenge.
Barca struggled away from the Nou Camp in Europe last term, scoring just once in three group stage matches and surrendering a 4-1 lead against Roma on a terrible night at the Stadio Olimpico to exit at the quarter-final stage.
Here's a detailed look at every player's performance on the night.
Zoet had to keep out a powerful Messi strike early in the second period as Barcelona started on the front foot.