For the first time in nearly a decade, Juventus has failed to advance from the Champions League group stage.
Rafa Silva scored twice as Benfica handed Juventus its fourth loss in five matches with a 4-3 win Tuesday to seal a spot in the knockout stage.
In a wild first half, Benfica got goals from Antonio Silva, Joao Mario and Rafa Silva while all Juventus could produce was a momentary equalizer from Moise Kean.
Silva - who recently announced his retirement from Portugal's national team and will not play at the upcoming World Cup in Qatar - added another goal early in the second half and also hit the post in the 86th.
Arkadiusz Milik pulled one back for Juventus in the 77th and Weston McKennie added another two minutes later, with both late goals set up by substitute Samuel Iling-Junior.
Paris Saint-Germain, which beat Maccabi Haifa 7-2 to also advance, and Benfica lead Group H with 11 points each. Juventus and Maccabi have three points each and will fight for third place and a Europa League spot.
Juventus visits PSG and Maccabi hosts Benfica in the final round of group matches next week.
It's the first time Juventus has failed to advance since the 2013-14 season.
The exit from Europe's top competition came a day after Juventus learned that club president Andrea Agnelli, vice president Pavel Nedved and CEO Maurizio Arrivabene are among 15 people placed under investigation for alleged false accounting and irregularities in player transfers following a notification from the public prosecutor's office in Turin.
Juventus issued a statement Wednesday denying any wrongdoing with its finances.
It's also an embarrassment for one of the few remaining clubs clinging onto the idea of a European Super League.
And Juventus faces a struggle to return to the Champions League next season. While the Bianconeri have won two straight in Serie A, they still sit in eighth place in the Italian league - with only the top four finishers qualifying.
Benfica went ahead 17 minutes in when 18-year-old center back Antonio Silva headed past surprise Juventus starter Federico Gatti.
Kean then scored from close range but had to wait while the goal was initially waved off for offside before the decision was overturned by the VAR.
A debatable handball from Juan Cuadrado set up a penalty for Joao Mario and then Silva converted a backheel flick after an exchange with Joao Mario.
Silva's second came when he sprinted past Leonardo Bonucci and chipped over the charging goalkeeper Wojciech Szczesny.