An alkaline composite PEO–PVA–glass-fibre-mat polymer electrolyte with high ionic conductivity (10−2 Scm−1) at room temperature has been prepared and applied to solid-state primary Zn–air batteries. The electrolyte shows excellent mechanical strength. The electrochemical characteristics of the batteries were experimentally investigated by means of ac impedance spectroscopy and galvanostatic discharge. The results indicate that the PEO–PVA–glass-fibre-mat composite polymer electrolyte is a promising candidate for application in alkaline primary Zn–air batteries.