Alkaline SPE was obtained from a blend of polyvinyl alcohol (PVA) and poly(epichlorohydrin) (PECH), PVA–PECH, by a solution-cast technique. The PVA host polymer is blended with PECH polymer to provide a polymer electrolyte with improved chemical and mechanical properties. The ionic conductivity of the PVA–PECH polymer electrolytes is between 10−2 and 10−3 Scm−1 at room temperature when the blend ratio is varied from 1:0.2 to 1:1. The PVA–PECH polymer was characterized by means of scanning electron microscopy, X-ray diffraction, stress–strain test, cyclic voltammetry, and a.c. impedance spectroscopy. It is found that the polymer electrolytes exhibit good mechanical strength and excellent chemical stability. The electrochemical performance of solid-state Zn–air batteries with various types of the blended polymer electrolyte films is examined by a galvanostatic discharge method.