Liverpool's youngsters battled hard against the Dutch league leaders but succumbed to a 3-2 defeat on the night. Elsewhere, Barcelona could only manage a draw which meant that the reds previous 7 consecutive victories ensured they finished the group stage two points clear, and ahead of all other 35 European clubs.
Arsenal and Aston Villa finished inside the top ten meaning they will go into the last 16 in March. Man City scraped through to the playoff round in February, where they will face Real Madrid or Bayern Munich.
Back in the country of Arne Slot's birth, he had opted to take a very much second string squad to Eindhoven.
Nine first team players remained at home, although Andy Robertson and Harvey Elliott where amongst the starters, and Cody Gakpo played for 50 minutes - grabbing a goal against his old club.
Jayden Danns was handed his first start in a Liverpool shirt but no goal this time for the youngster.
Cody Gakpo put the reds ahead after Federico Chiesa, who played the full 90 minutes, was felled inside the box. His celebration was muted out of respect for his former club.
PSV hit back when Bakayoko managed to put two Liverpool defenders on the ground, Robertson and Quansah sliding to try and stop the shot.
Chiesa was involved again in the 40th minute - his powerful shot could only force a parry from the PSV keeper and Elliott was there, four yards out, to give the reds the lead.
A half-time lead for Liverpool to enjoy? Perhaps not.
Saibari scored in the 45th minute from a tight angle before the reds were undone in the sixth minute of added time (VAR had signalled just the four) when Pepi made it 3-2.
The second half was much less eventful, with the reds bringing on more youth players to give them an opportunity. Amaro Nallo came on for the briefest of cameo's at centre-back but was given a red card for a clumsy challenge when he was (debatable) the last man.
At the final whistle however, the reds were confirmed as group winners, and will face either PSG, Monaco, Benfica, Brest.
A wonderful first group phase for Slot - but the hard work in this competition really does begin now.
MOTM: Federico Chiesa
VIDEO HIGHLIGHTS: PSV 3-2 LFC
