The Spanish side had already qualified for the last 16 but sealed top spot with a Lionel Messi strike and Gerard Pique’s clever second. Pique stabbed into the bottom corner in what looked like a planned move from Messi’s swept delivery, after the Argentine fired home through a crowd.
Luuk de Jong scored a late consolation for PSV, who missed a host of chances.
Jurgen Klopp’s side, who were beaten finalists last season, are third in Group C and need to beat first-placed Napoli at Anfield next month to have a chance of progressing, with the Serie A side defeating Red Star Belgrade 3-1 in the other game.
The Premier League side were outplayed for large periods of the game in Paris and James Milner’s penalty on the stroke of half-time was their only shot on target in a lacklustre showing.
By that point, they had already fallen two goals behind as Juan Bernat squeezed home the opener after Virgil van Dijk’s poor clearance, before Neymar started and finished a swift team counter-attack to double the advantage.
