Alkaline PVA polymer electrolyte with high ionic conductivity of about 0.047 S cm(-1) at room temperature was obtained by a solution casting method. The PVA polymer electrolytes, blended with KOH and H2O, were studied by DSC, TGA, cyclic voltammetric and a.c. impedance methods. The PVA polymer electrolytes show good mechanical strength and high ionic conductivity. The electrochemical stability window at the metal-electrolyte interface is +/-1.2 V for stainless steel. Ni-MH and Zn-air batteries with PVA polymer electrolytes were assembled and tested. Experimental results show good electrochemical performances of the PVA-based Ni-MH and Zn-air batteries.