Poly(vinyl alcohol) (PVA)/zeolite 4A mixed matrix composite membranes supported on polypropylene microfiltration membranes were prepared by solution casting method and crosslinked with glutaraldehyde to investigate their pervaporation (PV) separation properties of water–ethylene glycol mixtures. Scanning electron microscopy images showed homogeneous distribution of zeolite nanoparticles within the polymer matrix without any visible macroscopic voids at the zeolite–polymer interface. The PV experiments were accomplished to investigate the effects of water concentration (10–40 wt%) and temperature (60–80°C) on separation performance of the membranes. It was found out that 5 wt% loading of the 4A nanoparticles into the PVA matrix is optimal to obtain the best separation performance. The experimental results revealed that loading of zeolite 4A enhanced the membrane performance [both permeation flux (5%) and separation factor (32%) at 5 wt% zeolite loading]. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers