A microporous composite polymer membrane composed of poly(vinyl alcohol) (PVA) and poly(vinyl chloride) (PVC), was prepared by a solution casting method and a partial dissolution process. The characteristic properties of microporous PVA/PVC composite polymer membranes containing 2.5-10 wt.% PVC polymers as filters were characterized by thermogravimetric analysis (TGA), X-ray diffraction (XRD), scanning electron microscopy (SEM), capillary now porometry (CFP), micro-Raman spectroscopy, dynamic mechanical analyzer(DMA) and the AC impedance method. The electrochemical properties of a secondary Zn electrode with the PVA/PVC composite polymer membrane were studied using the galvanostatic charge/discharge method. The PVA/PVC composite polymer membrane showed good thermal, mechanical and electrochemical properties. As a result, the PVA/PVC composite polymer membrane appeals to be a good candidate for use oil the secondary Zn electrodes. (C) 2009 Elsevier B.V. All rights reserved.