Manchester City scraped into the play-offs, Lille gatecrashed the top eight and Liverpool finished at the summit despite losing after a breathless final night of the new-look Champions League group phase.
City, champions two seasons ago, trailed to Raphael Onyedika's goal for Club Brugge but second-half strikes from Mateo Kovacic and Savinho, either side of a Joel Ordonez own goal, saw them secure 22nd place in the 36-team table.
Incredibly, they will face either Bayern Munich or Real Madrid for a place in the last 16.
Lille qualified automatically in seventh, at the expense of AC Milan, with a thumping 6-1 win over Feyenoord.
The Dutch side scored three own goals - two from Gernot Trauner and another by David Hancko - while Osame Sahraoui, Jonathan David and Remy Cabella were also on target.
Morgan Rogers hit a hat-trick as Aston Villa secured eighth place with a 4-2 win over Celtic in the 'Battle of Britain'.
Republic of Ireland striker Adam Idah cancelled out Rogers' early brace with a quickfire double of his own, but Ollie Watkins put them back in front before Rogers completed his treble.
Champions League potential play-off and last-16 draw
- AS Monaco or Brest v PSG or Benfica in the play-offs. The winners will meet either Liverpool or Barcelona in the Round of 16.
- Sporting or Club Brugge v Atalanta or Borussia Dortmund in the play-offs. The winners will meet either Lille or Aston Villa in the Round of 16.
- Celtic or Manchester City will face Real Madrid or Bayern Munich in the play-offs. The winners will meet either Atletico Madrid or Bayer Leverkusen in the Round of 16.
- Feyenoord or Juventus will face AC Milan or PSV Eindhoven in the play-offs. The winners will meet either Arsenal or Inter Milan in the Round of 16.
Barcelona missed out on finishing top after they were held to a 2-2 draw by Atalanta.
Goals from Lamine Yamal and Ronald Araujo were not enough for Barca to climb above Liverpool, with the visitors twice pegging them back through Ederson and Mario Pasalic.
A point meant Atalanta dipped out of the top eight, finishing ninth.
Liverpool lost their 100% record in a 3-2 defeat by PSV Eindhoven.
Cody Gakpo and Harvey Elliott scored for the Reds but PSV won it through goals from Johan Bakayoko, Ismael Saibari and Ricardo Pepi.
Arsenal, Inter Milan, Atletico Madrid and Bayer Leverkusen made up the top eight.
The Gunners trailed to Arnaut Danjuma's goal for Girona but hit back to win 2-1 thanks to Jorginho's penalty and Ethan Nwaneri's strike.
Lautaro Martinez's hat-trick fired Inter to a 3-0 win over 10-man Monaco and Florian Wirtz and Nathan Tella helped Leverkusen to a 2-0 victory against Sparta Prague.
The draw to finalise the play-off and last-16 match-ups takes place on Friday at UEFA's headquarters in Nyon, Switzerland.
First legs of the play-off round will take place on 11/12 February, with the second legs on 18/19 February.
