Reina has been at Anfield since 2005, but spent last season on loan in Serie A with Napoli under Rafael Benitez, his former manager at Liverpool.
With Simon Mignolet established as Brendan Rodgers' first-choice, Reina's prospects of regular action at Liverpool appeared bleak.
And the 31-year-old is now set to join Bayern, where he can be expected to provide back-up to Germany number one Manuel Neuer.
A tweet from Bayern's official account on Tuesday read: "Goalkeeper Pepe Reina set for move from LFC to FC Bayern. [Chairman Karl-Heinz] Rummenigge confirms agreement. Medical to follow soon."
Rummenigge added: "Reina is a well-established, highly experienced player who meets the profile of the sport management.
"The player will come in the next few days for medical examination and to sign his contract."
Reina boasts 33 caps for Spain and played in his country's final group game, against Australia, at the recent World Cup.
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