A novel composite alkaline polymer electrolyte based on poly(vinyl alcohol) (PVA) polymer matrix, titanium dioxide (TiO 2) ceramic fillers, KOH, and H 2O was prepared by a solution casting method. The properties of PVA–TiO 2–KOH alkaline polymer electrolyte films were studied by X-ray diffraction (XRD), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), and AC impedance techniques. DSC and XRD results showed that the domain of amorphous region in the PVA polymer matrix augmented when TiO 2 filler was added. The SEM result showed that TiO 2 particles dispersed into the PVA matrix although some TiO 2 aggregates of several micrometers were formed. The alkaline polymer electrolyte showed excellent electrochemical properties. The room temperature (20 °C) ionic conductivity values of typical samples were between 0.102 and 0.171 S cm −1. The Zn–Ni secondary battery with the alkaline polymer electrolyte PVA–TiO 2–KOH had excellent electrochemical property at the low charge–discharge rate.