Monday evening’s draw paired the Premier League sides together in round five, to be played at Molineux across the weekend of March 7/8.
The tie comes just three years after they last clashed in the competition.
In January 2023, a 2-2 draw in the third round at Anfield was followed by a 1-0 victory for the Reds in the Molineux replay, where Harvey Elliott’s first-half strike from distance was the difference.
Four years earlier, Wolves prevailed at their home stadium in round three, eliminating Liverpool with a 2-1 result.
The Midlands club also beat the Reds 2-1, on that occasion at Anfield, when the sides faced off in the fourth round in January 2017.
By then, 65 years had passed since their previous FA Cup encounter.
On February 2, 1952, goals inside the opening 10 minutes from Bob Paisley and Cyril Done gave Liverpool a 2-1 victory over Wolves.