The Argentine midfielder would have no qualms playing in the backline in a competition he is eager to win, as it would be a massive boost for the season
The Liga champions are preparing for the first leg on Sunday with several injury worries at the back, as Gerard Pique sustained an injury in Wednesday's international friendly between Spain and Italy.
And with captain Carles Puyol currently recovering from knee surgery, it is believed coach Pep Guardiola will have to use an adapted centre-back, and Mascherano says he would have no problem filling in.
"I would prefer that all my team-mates were available to play, but if I am picked I will try do it the same way I did last year," he said at a press conference.
"The advantage is that I already have experience in that position."
Following the departure of Gabriel Milito to Independiente, it has been suggested that Barca boss Pep Guardiola could need another defender, but Mascherano has ruled out such scenario.
"He [Guardiola] trusts what he has. I am sad with Milito's departure because he is a great friend, but I know he is happy to be back with his family," he added.
The Argentine also signalled the importance of winning the Supercopa: "This is an important trophy and we want to win it because it will help us face the season with our confidence boosted."