A novel polyvinyl alcohol/hydroxyapatite (PVA/HAP) composite polymer membrane was prepared by the direct blend process and solution casting method. Glutaraldehyde (GA) was used as a crosslinker for the composite polymer membrane in order to enhance the chemical, thermal and mechanical stabilities and to reduce the swelling ratio. The characteristic properties of the PVA/HAP composite polymer membranes were examined by thermal gravimetric analysis (TGA), X-ray diffraction (XRD), scanning electron microscopy (SEM), micro-Raman spectroscopy and AC impedance method. Alkaline DMFC, consisting of an air cathode electrode with MnO2 carbon inks, an anode electrode with PtRu black inks on Ti-mesh matrix and the PVA/HAP composite polymer membrane, was assembled and investigated. It was found that the alkaline DMFC using a novel cheap PVA/HAP composite polymer membrane showed good electrochemical performance at ambient temperature and pressure.