The Europa League champions came from 4-1 down to force an additional 30 minutes, but wantaway striker Pedro netted the winner deep into extra time to cap off a memorable night in Tbilisi.
The showpiece, being played between two Spanish teams for the second consecutive year, was lit up by a free kick master class in the first half, with Ever Banega giving Sevilla a perfect start by curling his set piece into the top corner after just three minutes.
It didn’t take long for Lionel Messi to respond in kind to his compatriot, floating his own free kick over the wall and beyond the despairing dive of Beto just four minutes later.
The talismanic number 10 repeated the trick shortly afterwards too, again beating Beto from a set piece to see him score two direct free kicks in a match for the first time in his career.
That goal also took him to 24 against Sevilla – making them his favourite opposition – but it was his strike partner Luis Suarez who was the next to have the ball in the back of the net, although his finish just before the half-hour mark was controversially ruled out for offside.
A Dani Alves interception prevented Sevilla from creating a chance at the other end shortly before half time, and that proved decisive as Barcelona advanced up the pitch to score just two minutes later, Rafinha tapping home a Suarez cross after the Uruguayan had seen a shot of his own saved.
Suarez would get his own name on the score sheet less than 10 minutes after the restart, however, seemingly putting the game to bed by tucking a shot into the bottom corner having latched on to a Sergio Busquets through-ball.
Sevilla had other ideas, though, and they set about launching an unlikely comeback five minutes later as Jose Antonio Reyes tucked home a Vitolo cross to keep his side’s slim hopes alive.
Those hopes grew substantially 20 minutes from time when Jeremy Mathieu dragged Kevin Gameiro to ground into the box, and the Frenchman picked himself up to tuck the spot kick away.
Both sides exchanged chances over the next 10 minutes, with Messi being denied a hat-trick by Beto before Gameiro was inches short of connecting with a Coke cross.
The equaliser did come with just nine minutes remaining, however, as Yevhen Konoplyanka made it a dream debut by levelling things up from close range – a goal that made it the highest scoring Super Cup match in the competition’s history.
Having pegged three goals back in a half-hour spell against the reigning European champions, Sevilla began to retreat into their shells a little, and they were almost punished when Messi came within inches of bagging a hat-trick of direct free kicks.
Unai Emery’s side were able to force extra time, however, and the first period of the additional 30 perhaps understandably failed to live up to the frenetic pace of the previous 90.
It was the irrepressible Messi, still going despite his Copa America exploits, who had the first sight of goal in extra time, but his overhead kick from an Alves cross sailed over the bar.
However, it was Pedro – playing perhaps his final game for the club after handing in a transfer request with eye on Manchester United – who ultimately proved to be the difference, tucking home a rebound after Beto had denied a low strike from Messi.
There could have been yet another twist late on as Banega’s free kick found Coke, but the defender somehow couldn’t convert to make it 5-5, while Adil Rami also missed a golden opportunity with virtually the last kick of the match as Barcelona clung on.
The result sees Barcelona claim a record-equalling fifth Super Cup crown, drawing level with AC Milan as the most successful team in the competition’s history.