Bayern secured its place in German football history last season, as it became the first side to win the Bundesliga, DFB Pokal and Champions League in one campaign under the guidance of Jupp Heynckes.
Guardiola, who was announced as Heynckes' replacement in January before taking over in June, has designs on furthering Bayern's dominance of both German and European football after guiding Barcelona to three Liga titles and two Champions League crowns between 2008 and 2012.
Mario Gotze and Thiago Alcantara moved to the Allianz Arena in the offseason to bolster Guardiola's squad, but the Bavarians' start to the new campaign has been far from straightforward.
Bayern was fortunate to overcome Borussia Monchengbladbach on the opening day of the Bundesliga campaign and was held to a draw by Freiburg on Tuesday.
Now Bayern will renew acquaintances with the side that dealt the club one of its most bitter defeats, with Chelsea still carrying bragging rights from the 2011-12 Champions League final at Bayern's Allianz Arena.
Much has changed at Stamford Bridge since then, with Chelsea's place in the Super Cup coming after former interim manager Rafael Benitez helped rescue a disappointing 2012-13 season with victory in the Europa League. Now, Mourinho is in charge, with him opposing Guardiola for the first time since the two battled as rival Barcelona and Real Madrid managers in La Liga.
Mourinho has since returned for a second stint in charge with Chelsea, but, although the Portuguese has yet to lose a competitive game, recent performances against Aston Villa and Manchester United have been far from convincing.
Mourinho has almost a fully-fit squad to choose from for this game, with David Luiz - who has a hamstring injury - the only senior player expected to miss out as the Blues look to atone for last season's 4-1 thrashing by a Radamel Falcao-inspired Atletico Madrid.
Bastian Schweinsteiger (ankle) and Javi Martinez (abdominal injury) are both doubts for Bayern, while Thiago and Holger Badstuber (both knee) will both definitely miss out for Guardiola's side, who face an imposing challenge if it is to to add another trophy to the cabinet.