A composite polymer electrolyte, formed by dispersing into a poly(ethylene oxide)-lithium salt matrix two additives, i.e. calyx(6)pyrrole, (CP) acting as an anion trapper and superacid zirconia, S-ZrO2 acting as a conductivity promoter, has been tested as a separator in a new type of rechargeable lithium battery using lithium iron phosphate as the cathode. The choice of the electrolyte was motivated by its favourable transport properties both in terms of lithium ion transference number and of total ionic conductivity. The choice of the cathode was motivated by the value of its operating voltage which falls within the stability window of the electrolyte. The performance of the battery was determined by cycling tests carried out at various rates and at various temperatures. The results demonstrate the good rate capability of the battery which can operate at high charge-discharge efficiency even at 1  C rate and that it can be cycled at 90 °C with a satisfactory initial capacity of the order of 90 mAh g−1. These values outline the practical relevance of the composite electrolyte membrane and of its use as separator in a lithium battery.