Either Athletic Bilbao or Atletico Madrid lie in wait for the winners of Wednesday's tie, with the final set to take place on Sunday night.
Despite welcoming a number of their big-hitters back to the fold following a devastating coronavirus outbreak, Barcelona still came unstuck in league action at the weekend, as Granada rallied to rescue a point against the 10-man Blaugrana on Saturday night.
After Luuk de Jong had struck first for Barcelona and teenage sensation Gavi was sent for an early bath for two bookable offences, Granada's Antonio Puertas struck for his side in the 89th minute of the contest as a frustrated Xavi witnessed his side take just one point back to base.
La Blaugrana can forget about any sort of title charge this season, although the race to compete in Europe is one that they are very much in, and a priceless piece of mid-season silverware could present itself to Xavi's men in Saudi Arabia this month.
Barcelona have claimed a record 13 titles in the Spanish Super Cup but found themselves on the wrong end of a 3-2 scoreline against Athletic Bilbao last term - during which Lionel Messi saw red - and they also lost a five-goal thriller to Atletico Madrid the season before.
Xavi's men do enter the contest on a six-game unbeaten streak across all tournaments, but they have only kept one clean sheet in their last nine competitive matches in all competitions, and Real Madrid possess a certain 300-goal hero ready to expose such frailties.
Joining an elite crowd of players to have scored 300 goals for Real Madrid, the effervescent Karim Benzema once again stole the show for Real Madrid, who eased to a 4-1 success over Valencia in front of their own fans on Saturday.
Benzema's 300th strike for the club came via the penalty spot in the 43rd minute before Vinicius Junior capped off another fine display with a brace, and Benzema would put the result beyond any doubt with a fine turn and finish in the dying embers.
The former Lyon man has now followed in the footsteps of fellow 300-club members Alfredo Di Stefano, Raul and Cristiano Ronaldo, with his goals on the day taking Real Madrid that one step closer to top-flight glory before they turn their attention to proceedings in the Middle East.
Real Madrid's tally of 11 Super Cup titles can only be bettered by Barcelona - with their most recent success coming against city rivals Atletico in 2020 - but they also fell to Athletic Bilbao in the semi-finals of last year's competition.
The first El Clasico of the season ended with Los Blancos winning 2-1 at Camp Nou back in October - their fourth successive win over Barcelona - and Real Madrid also won 5-1 over two legs in the final of the 2017-18 Spanish Super Cup.
Barcelona defender Eric Garcia was taken off with a hamstring injury in the weekend's draw with Granada, and the former Manchester City man will now face up to five weeks out of action.
Garcia joins Sergi Roberto and Martin Braithwaite in the treatment room, but the previously COVID-positive duo of Pedri and Ferran Torres have been cleared to play alongside Frenkie de Jong, Ronald Araujo and Ansu Fati.
Gavi's suspension will instead carry over to his side's next La Liga clash, and Clement Lenglet will be ready to deputise for Garcia in the heart of the back four.
Carvajal could come straight back into the side over Lucas Vazquez if he is deemed fit enough, with the remainder of Ancelotti's backline remaining unchanged.
It would be a surprise to see the former Everton boss make many alterations from the side that saw off Valencia, with Federico Valverde - who famously hauled Alvaro Morata down when he was clean through on goal in the 2020 final - taking his place on the bench.
Barcelona possible starting lineup:
Ter Stegen; Dest, Pique, Lenglet, Alba; Gonzalez, Busquets, Gavi; Dembele, De Jong, Depay
Real Madrid possible starting lineup:
Courtois; Carvajal, Militao, Alaba, Mendy; Kroos, Casemiro, Modric; Asensio, Benzema, Vinicius Jr
We say: Barcelona 1-3 Real Madrid
With Benzema, Vinicius and a whole host of Real Madrid's XI playing out of their skin right now, a depleted Barcelona outfit cannot expect to head into Wednesday's semi-final as the favourites.
La Blaugrana will give it their all for a realistic shot at a trophy, but Ancelotti's free-scoring outfit possess the necessary firepower to march onto Sunday's final.
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