The Bavarians lost a penalty shootout in front of their own fans in Munich in May but the visit of Valencia will at least conjure happier memories of when they defeated the Spaniards in the 2001 final, the last time Bayern were crowned Kings of Europe.
Bayern have also had a break this season with a reasonably comfortable group that also includes Belarus's BATE Borisov and France's Lille.
With a string of signings, including Spaniard Javi Martinez for 40 million euros and in-form striker Mario Mandzukic, Bayern are hoping to bounce straight back.
"We will never forget that defeat, it was a hard knock but we have processed it," said defender Holger Badstuber. "This is a new chance to achieve something great."
With a perfect start to the Bundesliga season and three wins out of three games, Bayern look to have worked up an early appetite to avoid a repeat of the trophyless past season.
"Bayern were in the final last season and we deserve to be among the favourites this season," said Martinez, who is expected to make his competition debut. "That is why we want to start with a bang."
Coach Jupp Heynckes should have wingers Arjen Robben and Franck Ribery back in the squad after they missed Saturday's 3-1 win against Mainz 05 with minor injuries.
With Mario Gomez still recovering from surgery, Croatia forward Mandzukic, who has netted three goals in the league so far, is expected to remain their starting striker.
SLOW START
Valencia secured their first league win of the campaign under new coach Mauricio Pellegrino when they beat Celta Vigo 2-1 at home on Saturday, but it was far from convincing against a newly-promoted club.
Pellegrino, who replaced Unai Emery during the closed season, is still looking for his best side with a handful of new recruits, and they have yet to keep a clean sheet in their four games this term.
"The result helps but we didn't do that well and still have a lot of work to do," the Argentine said.
Pellegrino was a defender in the Valencia side that lost to Bayern in the 2001 final, and it was his spot-kick that was saved in the penalty shootout after extra-time that saw the title handed to the Germans.
Valencia have a number of injury problems with experienced midfielder David Albelda out with a hamstring problem and Argentina midfielder Fernando Gago still recovering from a blow to the head received on international duty last week.
Argentine forward Pablo Piatti broke his arm last week and joined long term absentees Ever Banega and Sergio Canales in the treatment room.
Probable teams:
Bayern Munich: 1-Manuel Neuer; 21-Philipp Lahm, 17-Jerome Boateng, 4-Dante, 28-Holger Badstuber; 30-Luiz Gustavo, 31-Bastian Schweinsteiger, 10-Arjen Robben, 25-Thomas Muller, 7-Franck Ribery; 9-Mario Mandzukic.
Valencia: 1-Diego Alves; 12-Joao Pereira, 4-Adil Rami, 18-Victor Ruiz, 3-Aly Cissokho; 24-Tino Costa, 21-Dani Parejo; 8-Sofiane Feghouli, 7-Jonas, 17-Andres Guardado; 9-Roberto Soldado.
