The two coaches were suspended following their involvement in an incident during last year's encounter, but can now guide their respective teams after all
Mourinho was handed a two-game ban last year after poking Vilanova in the eye during a touchline brawl in the 2011-12 Spanish Supercopa encounter at Camp Nou, while the new Blaugrana boss received a one-match suspension for his role in the incident.
However, the RFEF has now made the decision to allow both coaches to be in charge of their respective teams during this year's Supercopa.
Barcelona president Sandro Rosell recently stressed that he was against such a pardon, but the RFEF has nonetheless opted to lift the duo's bans.
The first leg is due to take place on August 21 at Camp Nou, with the return fixture scheduled one week later at the Santiago Bernabeu.