Last season's Champions League winners take on the Europa League holders at the Eden Arena in Prague in a star-studded contest between two of Europe's heavyweight sides
Bayern secured their place in German football history last season, as they 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.
Mario Gotze and Thiago Alcantara have moved to the Allianz Arena in the close-season to bolster Guardiola's squad, but the Bavarians' start to the new campaign has been far from straightforward.
Indeed, Bayern were fortunate to overcome Borussia Monchengbladbach on the opening day of the Bundesliga campaign, and were held to a draw by Freiburg on Tuesday.
Now Bayern will renew acquaintances with the side who dealt them one of their bitterest defeats at the Eden Arena, Prague, with Guardiola set to face off with Jose Mourinho, who guided Real Madrid as they snatched the Spanish title away from Barcelona in 2012.
Chelsea's last meeting with Bayern came in the 2012 Champions League final, with the Premier League side securing their first European crown in a penalty shoot-out at the Allianz Arena.
However, 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 UEFA Europa League.
Mourinho has since returned for a second stint in charge but, although the Portuguese has yet to lose a competitive game, recent performances against Aston Villa and Manchester United have been far from convincing.
The Portuguese 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.
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 they are to add another trophy to their cabinet.