Solid-state organic batteries based on charge-transfer complexes have been extensively used. However, the low mechanical strengths of these materials have restricted their applications. The polymer composite of these materials have been prepared and used in fabrication of solid-state batteries to overcome this problem. The pressed pellets of the polymer composite of o-tolidine–iodine (1:0.75) charge-transfer complex in poly(vinyl chloride) and polystyrene have been used as cathodes in contact with zinc as anode metal. The electrochemical characterization of these cells such as open-circuit voltages, short-circuit currents, their time and temperature dependence and rechargeability of these cells have been studied. The impedance analyses have been done to understand the nature of the electrode reaction.