The German has been hit with a two-match ban by Uefa's disciplinary panel for a dangerous tackle he made during Bayern's 3-3 draw with Ajax last month.
The 29-year-old was dismissed after catching Nicolas Tagliafico in the face with a high boot in the 75th minute of a thrilling group-stage clash in Amsterdam.
And the nature of the dismissal has prompted UEFA to extend Muller's ban beyond the mandatory one-match sanction.
Consequently, the Germany international will miss out on a trip to Anfield on February 19, and the return fixture against the Reds in Munich on March 13.
Earlier this week, Muller's teammate Arjen Robben described Liverpool as the 'worst possible draw' his side could have been handed.
“Liverpool is doing well again, just like last year when they made it to the final, and I also see them as a favourite for the Champions League victory this season," he said.
”For us, it was perhaps the worst possible draw, but it’s going to be a great challenge, we have to look at ourselves, keep working hard and improve ourselves.
"If we have a good day and play the way we want, I’m sure we’ll make it very difficult for Liverpool.”