The Blues, who won the Europa League last season, will face the Champions League winners with the Portuguese looking to improve his own personal record against Pep Guardiola.
Despite winning just three times in 15 meetings with the Bayern boss, Mourinho insists that facing the Bundesliga winners so early on in the campaign is good for his side.
"It's good for us," Mourinho told reporters. "Before we start the Champions League, it's very good to play with Bayern.
"I don't want players to feel that because we were successful in the Europa League, you can keep the same level and you can be successful in the Champions League, because it's a different planet.
"What I really feel is that in spite of a difference in experience between the two teams and the stability Bayern has - because over the last years they were basically the same team, the same players - we can compete against them. And when you compete eye to eye, it means you think you can win and we think we can."
The two sides meet in Prague at 7.45pm on Friday night.