Quaternized poly(vinyl alcohol)/chitosan (QPVA/CS) composite membranes were prepared by solution casting method with AlCl3·6H2O aqueous solution as solvent for CS and glutaraldehyde as a crosslinker. The crystalline, thermal and mechanical properties of the QPVA/CS composite membranes were studied by Fourier transform infrared spectroscopy, X-ray diffractometry, differential scanning calorimetry, thermogravimetry and tensile test measurements, respectively. The composite membranes were immersed in potassium hydroxide aqueous solution to form polymer electrolyte membranes. The alkaline uptake, swelling ratio, ion conductivity and methanol permeability of the electrolyte membranes were studied. The experimental results indicated that aluminum chloride hexahydrate (AlCl3·6H2O) had a positive effect on the mechanical properties of the QPVA/CS composite membrane. The elongation-at-break of this membrane reached the maximum of 401.0%. The alkaline uptake and swelling ratio of the composite membranes decreased. With the addition of 30 wt% AlCl3·6H2O, the composite membrane showed the ion conductivity and methanol permeability of 1.82 × 10−2 S cm−1 and 2.17 × 10−6 cm2 s−1, respectively. These values were higher than those of the membrane with acetic acid as the solvent for CS. The selectivity of the QPVA/CS membrane could reach 8.39 × 103 S s cm−3. This study showed that with AlCl3·6H2O as the solution for CS, the high performance QPVA/CS composite alkaline polymer electrolyte membrane could be prepared.