Napoli brought an end to Juventus's recent dominance in the Italian Super Cup with a dramatic sudden-death penalty shootout win in Doha.
Goalkeeper Rafael was the Napoli hero, saving Simone Padoin's effort after Kalidou Koulibaly had scored in the eighth set of spot-kicks.
In normal time, Carlos Tevez put Juve ahead before Gonzalo Higuain levelled.
Tevez's second looked to have won the game but Higuain struck again to set up the thrilling finish.
It gives Napoli some revenge for the 4-2 extra-time defeat they suffered against Juventus in this competition in 2012.
Juve also won the trophy last season as part of a haul of five domestic trophies in the last three-and-a-half years.
They can make it six if they claim a fourth straight Scudetto at the end of this campaign.
Massimiliano Allegri's side lead Serie A going into the winter break for the third year running, as they are three points above second-placed Roma.
They are also the only Italian team left in the Champions League and face a last-16 tie with German side Borussia Dortmund in February.
Monday was ultimately to be Napoli's night, though.
It was their involvement in a Champions League play-off against Athletic Bilbao in August that led to the Super Cup final being moved to mid-season from its traditional spot at the start of the campaign.
Rafa Benitez's Coppa Italia holders were beaten by Bilbao over two legs but proved they were no soft touch in Monday's Super Cup final, staged in Qatar for the first time after having previously been played in the US and China.
After falling behind to Tevez's cool finish following a defensive mix-up after just five minutes, they fought back, hitting the post twice - through a Marek Hamsik drive and a Higuain chip - before the latter headed them level in the second half.
Tevez looked to have won the game in extra time with his second of the game - a low shot into the bottom corner of the net - but with just three minutes to go, Higuain poked him his own second to send the game to penalties.
The two teams matched each other kick for kick in the shoot-out over eight sets of penalties - which included Tevez missing Juve's first and a run of four or saved penalties with the score at 5-5.
However, after Koulibaly slotted home his spot-kick, Rafael pushed away substitute Padoin's effort to decide the match.