Holders Porto produced a thrilling fightback to beat Chelsea 2-1 and grab a Champions League lifeline as Arsenal and Werder Bremen booked their places in the next round on Tuesday.
On a tension-filled night in Europe's premier club competition, Bremen beat Valencia 2-0 in a bad-tempered game at the Mestella and Arsenal thrashed Rosenborg Trondheim 5-1.
Nine teams had already qualified for the last 16, including Manchester United, Olympique Lyon, Juventus and Bayern Munich who play their final fixtures on Wednesday.
Nowhere was the drama more intense than on the banks of the River Douro where Porto looked set to become the first champions to fail to reach the knockout phase before a late winner from striker Benni McCarthy.
Chelsea coach Jose Mourinho, who left Porto after winning the UEFA Cup and Champions League in successive seasons to join the Premier League club, sat impassive as Ireland winger Damien Duff fired the Londoners ahead after 34 minutes.
Teenage Brazilian Diego levelled for Porto after 61 minutes with a superb volley but with CSKA Moscow leading 3-1 at Paris St Germain, Porto knew only a victory would save them.
South African McCarthy raised the roof four minutes from time, thumping a header past Petr Cech to inflict a first defeat on Chelsea, who had already qualified as Group H winners.
"They were the second best team in the group and deserved to go through," Mourinho said.
Chelsea finished with 13 points and Porto eight, while CSKA, for whom Sergei Semak scored a hat-trick in Paris, enter the UEFA Cup after coming third.
Arsenal needed victory to secure their place in the last 16 and early goals from Jose Antonio Reyes, Thierry Henry and Francesc Fabregas settled any nerves.
GOALKEEPING ERROR
A goalkeeping error by Spaniard Manuel Almunia, surprisingly chosen ahead of Germany's Jens Lehmann, gifted the visitors a goal but a Robert Pires penalty and a second-half effort by Robin van Persie completed the rout.
"As far as Europe is concerned the job is done," said Arsenal manager Arsene Wenger, whose side ended top of Group E. "It would have been very hard if we had gone out tonight."
PSV Eindhoven, who had already qualified, finished second after being hammered 4-1 at Panathinaikos, the Greek side earning the consolation of a UEFA Cup place.
With Inter Milan through in Group G, the significant action took place at the Mestalla Stadium in Spain, where Claudio Ranieri's Valencia needed to beat Werder Bremen 1-0 or by a two-goal margin.
The Spanish champions dominated and substitute Marco Di Vaio thundered a half-volley against the crossbar as Werder hung on grimly.
LATE DOUBLE
A late double from Paraguayan striker Nelson Valdez stunned the home side, however, and their misery was complete when midfielder Miguel Angel Angulo was sent off for an ugly challenge on Valdez.
An angry Ranieri, whose team can now concentrate on defending their UEFA Cup title, preferred to take his frustrations out on Swedish referee Anders Frisk.
"When you see the referee give them more than you, then you feel as though you were shafted," he said.
"Now I understand what happened to him at Roma when they hit him on the head," added Ranieri, referring to an incident this season during Roma's Champions League match against Dynamo Kiev.
Inter fielded a largely second-string side against Anderlecht but two goals from striker Obafemi Martins sealed top spot as the Belgians ended a miserable campaign without a point.
In Group F Shakhtar Donetsk claimed a UEFA Cup place with a 2-0 victory over a depleted Barcelona side, Nigerian forward Julius Aghahowa scoring both goals in the first half to see off the Spanish league leaders.
Barcelona finished second in the group, behind AC Milan who drew 0-0 at Celtic, a result that ended the Scottish club's participation in European competition this season.
The final four places in the knockout round are up for grabs on Wednesday, with the fate of nine-times champions Real Madrid still hanging in the balance.
The Spanish club must beat AS Roma in the Italian capital to guarantee their progression.
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