The anion-exchange composite polymer membrane based on quaterized poly(vinyl alcohol)/poly(epichlorohydrin) (designated as Q-PVA/PECH) was prepared by a solution casting method and a quaternization process. The characteristic properties of the Q-PVA/PECH anion-exchange composite polymer membranes were investigated by scanning electron microscopy, thermal gravimetric analysis, micro-Raman spectroscopy, and AC impedance method. Alkaline direct methanol fuel cells (ADMFC) comprised Q-PVA/PECH anion-exchange composite polymer membranes were assembled and examined. Experimental results indicate that an alkaline DMFC employing an inexpensive non-perfluorinated Q-PVA/PECH composite polymer membrane shows excellent electrochemical performances. The peak power densities of the DMFC using 4 M KOH + 1 M CH3OH, 2 M CH3OH, and 4 M CH3OH fuels are 17.22, 22.30, and 20.81 mW cm(-2), respectively, under ambient conditions. The Q-PVA/PECH composite polymer membrane appears as a viable candidate for use in an ADMFC.