A nanocomposite polymer membrane based on quaternized poly(vinyl alcohol)/fumed silica (QPVA/FS) was prepared via a quaternization process and solution casting method. The physico-chemical properties of the QPVA/FS membrane were investigated. Its high ionic conductivity was found to depend greatly on the concentration of fumed silica in the QPVA matrix. A maximum conductivity of 3.50 × 10−2 S/cm was obtained for QPVA/5%FS at 60 °C when it was doped with 6 M KOH. The permeabilities of methanol and ethanol were reduced with increasing fumed silica content. Cell voltage and peak power density were analyzed as functions of fumed silica concentration, temperature, methanol and ethanol concentrations. A maximum power density of 96.8 mW/cm² was achieved with QPVA/5%FS electrolyte using 2 M methanol + 6 M KOH as fuel at 80 °C. A peak power density of 79 mW/cm² was obtained using the QPVA/5%FS electrolyte with 3 M ethanol + 5 M KOH as fuel. The resulting peak power densities are higher than the majority of published reports. The results confirm that QPVA/FS exhibits promise as a future polymeric electrolyte for use in direct alkaline alcoholic fuel cells.