Liverpool topped the Champions League table despite losing 3-2 away from home against PSV Eindhoven on Wednesday evening.
A frantic first half saw Cody Gakpo open the scoring from the penalty spot after Federico Chiesa earned the Reds a spot kick nearly 30 minutes in, but PSV's Johan Bakayoko's individual brilliance brought the Dutch side level just minutes later.
Though Harvey Elliott restored Liverpool's lead near the half-time interval after more good work from Chiesa and Gakpo, late goals from Ismael Saibari and Ricardo Pepi gave the hosts a lead by the time the referee blew his whistle.
Barcelona's draw against Atalanta BC means Arne Slot's visitors finish in first place in the league phase with 21 points despite losing, and they will play one of Paris Saint-Germain, Benfica, Brest or Monaco in the round of 16.
Meanwhile, PSV have finished in 14th place with 14 points and must win a round of 16 playoff clash against either Juventus or Feyenoord in order to progress to the next round to play either Inter Milan or Arsenal.
SPORTS MOLE'S VERDICT
Slot spoke in the build-up to the match and argued that the result mattered little, but there will be some fans disappointed that the club missed out on the chance to be the first team ever to win all eight games in the league phase of the revamped tournament.
Regardless, the defeat can hardly have been unexpected given the Liverpool boss left out numerous senior players from his travelling squad, and it was clear that he was prioritising his team's fixture against Bournemouth on Saturday.
As for PSV, any victory against the Reds should not be taken for granted, and they now have the chance to set up a round of 16 clash against one of Europe's elite.
PSV EINDHOVEN VS. LIVERPOOL HIGHLIGHTS
Cody Gakpo goal vs. PSV Eindhoven (28th min, PSV Eindhoven 0-1 Liverpool)
Chiesa nips in front of Joey Veerman, who hacks the back of the Italian's leg in the box, and Gakpo sweeps home the resulting penalty into the bottom-right corner.
Gakpo scores against his former club!
Johan Bakayoko goal vs. Liverpool (35th min, PSV Eindhoven 1-1 Liverpool)
Pepi excellently controls a ball from the right channel with his chest near the edge of the box and tees up Bakayoko, who sits both Andrew Robertson and Jarell Quansah down by cutting back onto his right foot before striking home into the left side of the net.
Brilliant work by Bakayoko!
Harvey Elliott goal vs. PSV Eindhoven (40th min, PSV Eindhoven 1-2 Liverpool)
Gakpo controls a loose ball played in behind PSV's defensive line from Wataru Endo, and the Dutchman lays a pass off to Chiesa, who strikes at goal and see his effort rebound into the path of Elliott, and the Englishman finishes from close range on the left of the six-yard box.
He could hardly miss!
Ismael Saibari goal vs. Liverpool (45th min, PSV Eindhoven 2-2 Liverpool)
Endo loses possession in his own half and Veerman rushes through midfield before slipping in Saibari on the left of the penalty area, and he ferociously strikes in to the roof of the net past Caoimhin Kelleher.
What a finish!
Ricardo Pepi goal vs. Liverpool (45 + 6th min, PSV Eindhoven 3-2 Liverpool)
PSV counter-attack down Liverpool's right and get Mauro Junior is free to fire a low pass across the face of goal into the box, with the left-back finding Pepi, who flicks the ball past Kelleher.
PSV turn it around!
Amara Nallo red card vs. PSV Eindhoven (87th min, PSV Eindhoven 3-2 Liverpool)
PSV goalkeeper Walter Benitez plays kicks long behind Liverpool's defence, catching centre-back Nallo out, and the 18-year-old fouls Bakayoko to prevent him from running through to goal before receiving a red card on his full debut.
He was only on the pitch for four minutes!
MAN OF THE MATCH - RICARDO PEPI
Ricardo Pepi was instrumental in PSV's comeback, scoring his side's winning goal, assisting his side's first and creating two chances, the joint second most of any player.
Bakayoko deserves plaudits for scoring the first of his team's three goals against Liverpool, but it was Pepi's outrageous control and layoff that turned the situation into a threatening chance in the first place.
PSV EINDHOVEN VS. Liverpool MATCH STATS
Possession: PSV Eindhoven 53%-47% Liverpool
Shots: PSV Eindhoven 12-9 Liverpool
Shots on target: PSV Eindhoven 5-5 Liverpool
Corners: PSV Eindhoven 8-2 Liverpool
Fouls: PSV Eindhoven 11-11 Liverpool
BEST STATS
WHAT NEXT?
PSV will next face NEC Nijmegen on February 1 in the Eredivisie before before taking on Dutch giants Feyenoord in the KNVB Beker on February 5.
Liverpool return to Premier League action on Saturday when they face Bournemouth away from home, and the Reds then host Tottenham Hotspur at Anfield in the second leg of the EFL Cup semi-final on February 6.