Showing the instincts of a striker, Provedel rescued Lazio as he leapt to meet an inswinging cross from Luis Alberto, guiding a powerful glancing header past Atletico counterpart Jan Oblak at the Stadio Olimpico in Rome.
The scarcely believable moment saw Provedel become just the sixth goalkeeper to score a goal in Champions League history, and only the second from open play. Provedel was also making his first appearance in the Champions League and his header was the final touch in the match.
The Italian was quickly surrounded by his stunned teammates, while Provedel did not even break into a smile while celebrating as he was chased by substitutes running onto the pitch.
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"I’m going to enjoy this. But we only got one point, we didn’t win," Provedel said.
The 29-year-old said he modelled his attacking style after Lazio striker Ciro Immobile.
Lazio fell behind in the first half of their Champions League opener after Pablo Barrios scored for Atletico with a goal that took a big deflection past Provedel.
There was also drama in the other Group E encounter as goals from Calvin Stengs and Alireza Jahanbaksh saw Feyenoord claim a 2-0 win over Celtic, who finished the game with nine men.
Stengs’ free-kick snuck home to give the Dutch side the lead on the stroke of half-time and Brendan Rodgers’ men unravelled after the interval as both Gustaf Lagerbielke and Odin Thiago Holm saw red.
Osman Bukari fired the visitors in front against the run of play just before half-time but it took Alvarez 72 seconds of the second half to slide his side back in front.
Alvarez had a say in City’s second as his free-kick was flapped into his own net by Red Star keeper Omri Glazer, and Pep Guardiola’s men wrapped up a deserved victory when Rodri produced a typically composed finish 17 minutes from time.
Also in Group G, substitute Benjamin Sesko scored in injury time to seal a 3-1 win for RB Leipzig at Young Boys.
The Portugal international fired an 11th-minute opener before Robert Lewandowski added his side’s second on 19 minutes for Xavi’s in-form side.
The visitors, returning to the top level of European football for the first time in 65 years, fell further behind after 22 minutes when Jelle Bataille’s unfortunate deflection flew in off the post.
Barca were in cruise control with teenager Gavi adding his side’s fourth goal nine minutes into the second half before the outstanding Felix deservedly completed the rout with his second just past the hour mark.
Two goals from Galeno helped Porto begin their Group H campaign with a 3-1 win over Shakhtar Donetsk in Hamburg.
Kylian Mbappe opened the scoring from the penalty spot as Paris Saint-Germain kicked off their Group F campaign with a 2-0 win over Borussia Dortmund.
The hosts had to wait until the 49th minute for their opener but made sure of the points in the 56th minute when Achraf Hakimi doubled their advantage with a quality finish.
The Portugal international had only keeper Nick Pope to beat after a surging 34th-minute run but attempted an audacious flick and only succeeded in tripping himself.
Pope made a series of fine first-half saves to earn a point for the Magpies in their first top-level European match for 20 years, but the frustration was clear among the fans of the seven-time winners.
Includes reporting from PA