While the Spaniards, who finished fourth in La Liga last season, host Germany's record champions, who finished a disappointing third in the Bundesliga, the group's other two participants Manchester City and Napoli will be locking horns in England.
With little to choose between all four clubs as they take their places in the starting blocks, avoiding a false start is a priority.
"Spanish football is the best that Europe has to offer at the moment," said Bayern's chairman Karl-Heinz Rummenigge to reporters before Munich flew out to Valencia on Tuesday.
"We know that the final takes place in Munich and we have got to pay attention that such a dream does not turn into a nightmare.
"We need to concentrate to ensure that we don't experience any setback."
The prospect of taking part - and winning - the final in their own stadium is the driving force behind Bayern's motivation while Villarreal are just keen to enjoy the occasion alongside three of European football's giants.
"Playing in this competition is the biggest stimulus a footballer could have nowadays," said their coach Juan Carlos Garrido.
"We know that we have been dealt a difficult group with three of the best sides in the world right now, but this is the Champions League.
"We face three clubs who attract an immense media interest and with players from the highest level.
"For Villarreal, it is magnificent to be able to play in this competition against teams with such history.
"Playing against Bayern is a great motivation."
However, Garrido insists his side will not only be making up the numbers Wednesday night.
"We are going to have to fight for every ball and get the fans on our side," he added.
"We know that they are a good team and we are going to have to work very hard because this is a crucial game.
"To keep the three points would be a major coup and it would make our intentions clear that we can qualify."
A 2-2 draw with Sevilla saw Villarreal get their first point of the season in La Liga at the weekend while Bayern warmed up for Wednesday night's clash with a 7-0 win over Freiburg.
However, their coach Jupp Heynckes is reading little into that victory.
Although that emphatic result will have "given us a boost", Heynckes has warned Wednesday's opponents will certainly provide a much sterner test.
"European games cannot be compared with the Bundesliga," he said.
Bayern will be without Arjen Robben, whose groin injury is proving to be more problematic than first feared.
It is likely Heynckes will name the same starting XI as he did on Saturday with in-form Mario Gomez, who has scored seven goals in his last two games, leading the attack with Franck Ribery and Thomas Muller in support.
Garrido is without the suspended Borja Valero, who was sent off in the qualifying match against Odense, while Cristian Zapata is also part of the squad after missing the Sevilla game due to a late return from international duty with Colombia.