A win for the Bavarians would take last season's beaten finalists through to the last 16 with a game to spare, while victory for Valencia without conceding - or by more than a single goal - would guarantee them one of the two qualifying berths and leave Bayern sweating.
A draw, on the other hand, would only serve to do Bayern a favour, being enough to see them through if BATE Borisov slip up against Lille, but the Germans are focusing on getting all three points on Tuesday night.
"We want to win the group," said chairman Karl-Heinz Rummenigge prior to departure.
Bayern's hopes may be compromised somewhat by the rib injury to Franck Ribery which could deprive them of their "best player", according to Rummenigge.
"He's a key player for us," he said. "Take Lionel Messi out of Barcelona or Cristiano Ronaldo out of Real Madrid, or Wayne Rooney out of Manchester United and they are not the same.
"They are dependent on those players and our game is dependent on Ribery."
"He has been the best player for us in recent months and when he's on the field, it's good for our team and not so good for our opponents, so I hope he can play tomorrow [Tuesday].
Valencia will certainly be keeping their fingers crossed that the Frenchman wakes up with his ribs still too sore to play, although they prefer to concentrate on their own strengths.
Mauricio Pellegrino's men have won their last seven competitive matches at the Mestalla, including Champions League triumphs over BATE and Lille, while they have only lost once in 15 games in front of their own fans since March.
"It's a very important game for the club and the fans, but we're ready to have a good game," said defender Adil Rami.
"We know that they are one of the best teams in the world, but we shouldn't forget that at home we're looking unbeatable.
"Here we have our best weapons."
Valencia were not so impressive in defeating the Primera Division's bottom club Espanyol at home this weekend, needing a last-gasp penalty from Roberto Soldado to claim a 2-1 triumph, but Rami is consoled by the fact they got the three points.
"Everyone, all the Valencia players, did poorly," the France international admitted.
"When we play well and lose, it's bad, but when we play badly and we win, at least we get the three points.
"In any case, there's plenty of motivation for tomorrow's [Tuesday's] game, because it's at our ground, because it's against one of the best sides in the world, because it is a Champions League game.
"It has everything."
Pablo Piatti, Sergio Canales, Fernando Gago and Jeremy Mathieu are all unavailable to Valencia.