Novel alkaline solid polymer electrolyte membranes that can conduct anions (OH-) have been prepared from poly(vinyl alcohol)/poly(vinylpyrrolidone) (PVA/PVP) by blending and chemical cross-linking, followed by doping in aqueous KOH solution. The physicochemical properties of these membranes have been studied in detail by FTIR. TG, and SEM analyses. The ionic conductivity was found to be greatly dependent on the concentration of KOH and the interpenetrated PVP in the PVA matrix. A maximum conductivity of up to 0.53 S cm(-1) at room temperature was achieved for PVA/PVP in a mass ratio of 1:0.5 after doping in 8 M aqueous KOH solution. The membrane showed perfect alkaline stability without losing its integrity even upon exposure to 10 M KOH solution at up to 120 degrees C. Scanning electron micrographs revealed a highly ordered microvoid structure uniformly dispersed on the membrane surface with a pore size of ca. 200 nm after heat-curing, which imparted the membrane with good liquid electrolyte (KOH) retention ability. FTIR spectra showed that these high ionic conductivities may be attributed to the presence of excess free KOH in the polymer matrix in addition to KOH bound to the polymer. Almost constant, highly stable, ionic conductivity while maintaining mechanical integrity was retained at room temperature for more than one month. (C) 2010 Elsevier Ltd. All rights reserved.