German qualifier Zverev beat compatriot Jan-Lennard Struff 7-6 (8/6) 3-6 6-4 in the first round on Tuesday to set up the clash with top-seed Murray, who received a bye into round two.
That match will take place on Thursday, although Murray will actually be on court on Wednesday in the doubles competition. He is partnering Dutchman Jean-Julien Rojer as he looks to get some claycourt match practice under his belt.
Meanwhile, two-time winner Philipp Kohlschreiber progressed with a straight-sets victory over Jiri Vesely of the Czech Republic.
Kohlschreiber, who did not have to face a break point, was a 6-1 6-2 victor but compatriot Dustin Brown is out after he lost 6-1 7-6 (7/2) to Italian Simone Bolelli.
Former top-10 star Janko Tipsarevic continued his return from a long-term injury by defeating number six seed Bernard Tomic 5-7 6-1 7-6 (7/3).
There were also wins for Lukas Rosol, Fabio Fognini, Dominic Thiem, Sergiy Stakhovsky and Radek Stepanek, another player on the way back from injury.