Carlo Ancelotti's side could only finish in second place behind Atletico Madrid in the group stages, meaning they must host Arsene Wenger's men when their last-16 tie gets underway next Wednesday.
Bayern dealt out a 5-1 thrashing to Arsenal during the round-robin phase last season but, despite holding a four-point advantage at the top of the Bundesliga, they have rarely convinced to such an extent this time around.
Muller scored 32 goals in all competitions last term but, remarkably, the Germany star has a solitary league goal to his name this season.
The 27-year-old hopes renewing acquaintances with Premier League opponents will help to spark an upturn in performance.
"The games against Arsenal are very important for the mood in the Bayern camp for the remainder of the season," he said, as quoted by Sport Bild.
"Knockout games are always very explosive. It's where ambition meets reality and people are bound to get annoyed when these two lie far apart.
"I am very hungry to play games like these."
First up is a trip to second-bottom Ingolstadt in the Bundesliga on Saturday and Muller knows Bayern must not become distracted by the Arsenal showdown just yet.
"We now have a difficult game against Ingolstadt coming up first, it will be tricky," he added, having been an unused substitute for Tuesday's 1-0 DFB Pokal win over Wolfsburg.
"Those are the sort of games that are the toughest ones to win."