In this study, composite polymer electrolytes were prepared by addition of titanium oxide, TiO2 nanofiller into polyvinylidene fluoride-co-hexafluoropropylene/polymethyl methacrylate-ammonium triflate (PVDF-HFP/PEMA-NH4CF3SO3) complex. The effect of TiO2 on conductivity of the complex was examined using impedance spectroscopy. The highest room temperature conductivity of 1.32 × 10-3 S cm-1 was shown by the system containing 5 wt % of TiO2. This system was used for the fabrication of proton batteries with the configurations of (Zn + ZnSO4.7H2O + C + PTFE)/PVDF-HFP/PEMA-NH4CF3SO3-(5wt%)TiO2/(MnO2 + C + PTFE) and (Zn + ZnSO4.7H2O + C + PTFE)/PVDF-HFP/PEMA-NH4CF3SO3-(5wt%)TiO2/(MnO2 + PbO2 + C + PTFE). The performance of the batteries indicated potential application of the electrolyte system in proton batteries.