Fred was the villain as Manchester United failed to secure their place in the last 16.
The United midfielder was sent off in the 70 minute for a second yellow card as United slumped to defeat at Old Trafford.
The loss means United must now avoid defeat away to RB Leipzig next Tuesday to ensure they progress to the knockout stage.
Ole Gunnar Solskjaer's failure to replace Fred at half-time, after he somehow escaped a red card for a head-butt on Leandro Paredes, ultimately cost United.
Fred was eventually sent off for a second yellow card, leaving 10-man United little chance of coming back from 2-1 down.
Nemyar opened the scoring early on, but Marcus Rashford brought United level, only for Marquinhos to re-establish PSG's lead.
United's fate was sealed in the first minute of added time when Neymar made it 3-1 with his second of the game,.
That means Group H will go down to the wire, with United, PSG and Leipzig all on nine points and United in Germany for their final game.
Manchester United player ratings
David de Gea 7
Fine save from Florenzi. Even better from Bakker at 1-1. Little chance of stopping Marquinhos goal.
Aaron Wan-Bissaka 6
Played everyone onside for PSG's second goal. Had his work cut out defensively.
Victor Lindelof 6
Made some timely blocks and interceptions, despite some wayward passing early on.
Harry Maguire 6
Vocal at the back as he marshalled his side. But was also caught out for PSG's opener.
Alex Telles 5
Too slow to react for Neymar's opener. Not as much of an attacking threat as in recent games.
Should have been sent off for head-butt on Paredes. Eventually was for a second yellow card.
Scott McTominay 7
Relished his battle with Neymar and came out on top, playing with courage and belligerence.
Bruno Fernandes 7
Tried to inspire United once again and had some nice touches, but lacked usual influence.
Anthony Martial 6
His shot was saved in move that led to United's equaliser. Shocking miss just after the restart.
Edinson Cavani 6
Kept his place after two-goal heroics at the weekend. Hit the bar with sublime chipped effort.
Marcus Rashford 7
Industry rewarded with equaliser, taking his Champions League total to six goals this season.
PSG: Navas 6; Florenzi 7, Marquinhos 7, Diallo 6, Kimpembe 6; Veratti 7, Danilo 7, Paredes 6 (Herrera 64, 6), Neymar 7, Kean 6 (Bakker 64, 6), Mbappe 7
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