The last-16 first-leg clash will be the first meeting of the two continental heavyweights, who have each won the European Cup on five occasions, since the Reds beat Bayern in the final of the UEFA Super Cup back in 2001.
Niko Kovac's Bundesliga champions qualified for the knockout stages of this season's competition by topping Group E ahead of Ajax, Benfica and AEK, while Jürgen Klopp's men finished second in Group C, behind Paris Saint-Germain, and ahead of Napoli and Red Star Belgrade.
Both sides currently sit second in their domestic leagues and seem closely matched heading into this contest. We've picked out three key battles that could help decide the game...
Sadio Mane v Joshua Kimmich
Versatile Germany international Kimmich has played more minutes under Bayern boss Kovac than any other player this season, including every second of their Champions League campaign thus far.
Predominantly used at right-back this term, the 24-year-old is equally adept playing as a midfield pivot and initially made the breakthrough in Munich as a makeshift centre-back under Pep Guardiola, who insisted Kimmich had the quality to play in any position.
Tipped off by his former boss Guardiola, Barcelona legend Xavi Hernandez has been following Kimmich's career closely and after meeting the player at a Doha training camp last month said: "He can be one of the best players in world football in several positions, maybe he already is."
Ball-playing Kimmich, who leads Bayern with 13 assists this season, is expected to eventually end up in midfield as a No.6, but it's his defensive fortitude at full-back that is sure to be put to the test at Anfield when he comes up against an in-form Mane.
Liverpool's Senegalese forward has scored in each of his last four games and is only behind Mohamed Salah in the club's scoring charts for the season.
Usually starting from the left flank, the No.10 has developed the happy knack of claiming crucial goals.
Mane bagged Liverpool's last - which proved to be the winner - in the thrilling 4-3 victory against Crystal Palace last month, scored the Reds' single strikes in a pair of 1-1 draws with Leicester City and West Ham United, and netted the opener to initiate a 3-0 win over Bournemouth last time out.
Georginio Wijnaldum v Leon Goretzka
Signed from FC Schalke in the summer, Germany international Goretzka has become an integral part of Kovac's central midfield - often playing in tandem with Spain international Thiago at the base of a 4-2-3-1 formation.
The 24-year-old, who says he models his game on the likes of Bastian Schweinsteiger and Toni Kroos, has the ability to score goals from deep and pick out key passes for his teammates - notching six goals and four assists this season.
His box-to-box role can make him hard to pick up as he can drop deep or move further forward to find gaps as the game dictates. If Goretzka does find space in the final third, expect to see a long-range shot - one of his specialities.
Looking to shut down the young German and exert his own influence on the tie will be Liverpool's Dutch midfielder Wijnaldum, who is not dissimilar to his potential opponent in his ability to play as either an attacking or more defensive option.
The 28-year-old began the season having transitioned into a traditional No.6 role, as the deepest man in midfield, but in recent fixtures he's reverted to a position further up the pitch.
In last Saturday's 3-0 win against Bournemouth, the Netherlands international was the most advanced midfielder in a 4-3-3. He set up three goalscoring opportunities for his teammates, enjoyed a 91 per cent pass completion rate and scored an exquisite lob after breaking forward to connect with Andy Robertson's lofted pass.
If Wijnaldum can replicate his attacking repertoire at Anfield on Tuesday, he will almost certainly cause problems for Goretzka and Thiago.
Joel Matip v Robert Lewandowski
This battle promises to renew an old rivalry from German football's Ruhr derby, when Matip's Schalke battled Lewandowski's Borussia Dortmund for regional bragging rights.
The duo faced off seven times in all competitions during this four-year period and shared the spoils equally - winning three each and drawing one.
Lewandowski secured his high-profile move to Bayern in 2014 and gained the advantage in their head-to-head before Matip joined Liverpool two years later.
The Reds defender will certainly know all about his opponent's game heading into this clash, as will manager Jürgen Klopp, who mentored the Poland international during his time in Dortmund. Stopping Lewandowski, however, is another matter.
He has been Bayern's top scorer in each of the last four seasons - 2017-18 (41), 2016-17 (43), 2015-16 (42), 2014-15 (25) - and the 6ft 1in forward is top of the tree again this term, and by quite some distance, with 25 strikes so far.
A classic No.9, the 30-year-old conducts most of his business in and around the box, where his natural sense of positioning, awareness and deadly finishing with either foot, or aerially, make him prolific.
Usually deployed as a lone centre-forward, shackling Lewandowski would go a long way to blunting Bayern's attack. Matip's familiarity with his old foe might make him best placed to do just that.
The centre-back has played every minute of Liverpool's last four matches after returning from a broken collarbone fresh and rested.
He led the team with 11 clearances and two interceptions as Liverpool kept a clean sheet against Bournemouth last time out and his return to form is perfectly timed with Virgil van Dijk suspended for this match.