Membrane separators are one of the critical components in zinc–air batteries (ZABs). In the control of mass transfer, and hence, electrochemical reaction, membrane separators have an important role to play. This work addresses the issue of battery performance in a ZAB via a new composite membrane separator based on polyvinyl alcohol (PVA). To enhance the electrolyte uptake and ionic conductivity, mesoporous Mobil Composition of Matter No. 41 (MCM-41) is incorporated as a filler in the membrane while maintaining its integrity. The presence of MCM-41 is seen to reduce the number of cycles of secondary ZABs due to the uninvited drawbacks of increased zincate crossover and reduced triple phase boundary at the air cathode, which is pivotal for oxygen reduction reaction. Overall, results suggest that the application of the MCM-41/PVA composite has the potential for use as a separator in high-capacity primary ZABs.