From Barcelona's recovery at Camp Nou to shock defeats in Madrid and famous wins elsewhere, the latest round delivered decisive moments at both ends of the table.
Barcelona hit back to see off Copenhagen
Barcelona booked their place in the last 16 with a 4-1 win over Copenhagen at Camp Nou, extending their strong home form in all competitions.
The Catalans were stunned early on when Viktor Dadason fired the visitors ahead inside four minutes, but Barcelona gradually took control with patient possession and sustained pressure.
Their breakthrough came shortly after the restart when Robert Lewandowski finished from close range following a swift move involving Lamine Yamal.
Yamal then put Barcelona in front with a deflected effort just after the hour mark, before Lewandowski won a penalty that Raphinha confidently converted.
Marcus Rashford capped a comfortable finish with a late free-kick as Barcelona sealed qualification and left Copenhagen eliminated despite their disciplined first-half display.
Benfica stun Real Madrid in extraordinary finish
Real Madrid were forced into the knockout play-offs after a dramatic 4-2 defeat away to Benfica, a match settled by a remarkable late goal from goalkeeper Anatoliy Trubin.
Kylian Mbappe opened the scoring for Madrid with a close-range header, but Benfica responded quickly through Andreas Schjelderup. Vangelis Pavlidis then put the hosts ahead from the penalty spot just before half-time.
Schjelderup struck again early in the second half, only for Mbappe to level with his second goal of the night.
The game swung decisively in added time as Real Madrid were reduced to nine men, and with virtually the final kick, Trubin rose highest to head home from a free-kick and send Benfica through in dramatic fashion.
Bodo-Glimt shock Atletico Madrid in Spain
Bodo-Glimt claimed one of the results of the competition by beating Atletico Madrid 2-1 at the Metropolitano to secure a historic place in the knockout stage.
Atletico took the lead through Alexander Sorloth, but the Norwegian side responded against the run of play when Fredrik Sjøvold finished calmly from inside the area. Despite heavy pressure from the hosts, Glimt stayed in the contest and struck again just before the hour mark as Kasper Høgh capitalised on defensive confusion.
Atletico pushed hard for an equaliser but lacked precision, ending their long home winning run and leaving them to settle for a seeded play-off place.
Sporting strike late to break Athletic hearts
Sporting CP secured a top-eight finish and direct passage to the round of 16 with a dramatic 3-2 away win over Athletic Club.
Athletic twice took the lead through Oihan Sancet and Gorka Guruzeta, but Sporting showed resilience, levelling first through Ousmane Diomande and later via Francisco Trincao after a sharp move.
With the hosts pushing for the goal they needed, Sporting struck in added time as Alisson Santos fired low into the corner to seal victory and confirm their automatic qualification.
Tillman double sends Leverkusen into play-offs
Bayer Leverkusen wrapped up a knockout round play-off place with a convincing 3-0 home win over Villarreal.
Malik Tillman scored twice in the first half, the opener coming after his press forced a defensive error, before a precise finish from the edge of the area doubled the lead. Alejandro Grimaldo added a third after the break to complete a dominant display.
The result confirmed Leverkusen's progression, while Villarreal exited the competition after finishing near the bottom of the league phase.
The night underlined just how fine the margins remain in the Champions League, with giants tested, underdogs rising, and qualification decided in the most dramatic fashion.