Veteran midfielder Andrea Pirlo uncharacteristically missed a penalty in San Francisco, which would have clinched victory for Juventus in the shootout, and Everton goalkeeper Tim Howard saved Federico Peluso's spot-kick soon after to hand Roberto Martinez's team the win.
After a goalless first half at AT&T Park, Everton took a deserved lead in the 61st minute when Victor Anichebe and Darron Gibson's good work in midfield allowed Kevin Mirallas to burst in from the right wing and score.
Juventus equalised with 10 minutes remaining as Kwadwo Asamoah brilliantly thrashed Mirko Vucinic's cut-back into the top corner but Everton eventually triumphed in the shootout.
Everton looked to have opened the scoring in just the fifth minute when Steven Pienaar's free-kick curled into the far corner of Marco Storari's net but Martinez's team were denied the goal because Phil Jagielka was judged offside, despite not quite touching the ball as he ran across Juventus' goalkeeper.
The English Premier League club had the better of the first half in terms of possession but had to wait until the final two minutes for their next big chance.
Mirallas' free-kick was deflected by a Juventus defender straight to John Stones and the 19-year-old defender's header struck the post.
Having held out to half-time without conceding, Juventus started the second half brightly with Carlos Tevez getting into the game and linking well with Fernando Llorente and Arturo Vidal on a couple of occasions.
Llorente teed up Mauricio Isla but the Chilean hit the side netting, before Vidal's fine free-kick was pushed away from the bottom corner by Everton goalkeeper Tim Howard.
But just after the hour mark, Everton took the lead with Anichebe, who was one of his side's best, winning the ball in the centre circle off Luca Marrone and starting an attack that finished with Mirallas scoring at the near post.
Everton's goal seemed to spark Juventus with Llorente having a shot blocked on the line eight minutes later and Howard smothering Vidal's follow-up effort, while Tevez thrashed a shot just wide of the post.
The introduction of Vucinic and Andrea Pirlo in the 71st minute made a significant difference for the Serie A club with the former setting up Juventus' equaliser nine minutes later.
In the 90th minute, Everton had the best chance to win the match with Ross Barkley's swerving strike from long range forcing Storari into an unorthodox save with his knees.
Storari saved Everton's opening penalty to give Juventus the advantage in the shootout but after a string of successful spot-kicks, Pirlo pulled his wide to ensure sudden-death penalties.
After successful penalties from Stones, Marco Motta and Bryan Oviedo, Howard got two hands to Peluso's effort and Everton claimed the win.
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