Juventus won the second leg in Turin 3-2 over FC Porto after extra-time but the Portuguese had won the first leg 2-1 at home, meaning it finished tied 5-5 on aggregate, with the Dragons edging ahead on away goals.
It was a dramatic second leg as Porto took a 19th minute lead from Sergio Oliveira’s penalty, but Federico Chiesa got the Old Lady back into it with a second-half double either side of Mehdi Tarami’s needless second yellow card.
Despite playing for half an hour with 10 men, Porto forced the match into to extra-time where Sergio Oliveira’s long-range drilled free-kick went under the Juve wall and beat Wojciech Szczesny in the 115th minute.
The goal set off wild scenes of celebrations for Porto, with Juve requiring two goals now to win the tie, although they hit back instantly with an Adrien Rabiot header but they couldn’t find a winner.
The defeat caps another disappointing UEFA Champions League campaign for Juve, particularly since Ronaldo’s arrival in 2018.
The Italian champions have crashed out in the last 16 in the past two seasons, while in 2018-19 they were knocked out in the quarter-finals.
Elsewhere, Erling Haaland scored a double as Borussia Dortmund booked their quarter-final spot with a 5-4 aggregate win over Sevilla despite a 2-2 second leg draw.
Dortmund had been cruising at 2-0 up but Sevilla fought back with a Youssef En-Nesyri brace ensuring a tense final few minutes.