The characteristics of polyaniline/graphite composites (PANi/G) have been studied in aqueous electrolyte. PANi/G films with different graphite particle sizes were deposited on a platinum electrode by means of cyclic voltammetry. The film was employed as a positive electrode (cathode) for a Zn-PANi/G secondary battery containing 1.0M ZnCl2 and 0.5M NH4Cl electrolyte at pH 4.0. The cells were charged and discharged under a constant current of 0.6mAcm−2. The assembled battery showed an open-circuit voltage (OCV) of 1.55V. All the batteries were discharge to a cut off voltage of 0.7V. Maximum discharge capacity of the Zn-PANi/G battery was 142.4Ahkg−1 with a columbic efficiency of 97–100% over at least 200 cycles. The mid-point voltage (MPV) and specific energy were 1.14V and 162.3Whkg−1, respectively. The constructed battery showed a good recycleability. The structure of these polymer films was characterized by FTIR and UV–vis spectroscopies. Electrochemical impedance spectroscopy (EIS) was used as a powerful tool for investigation of charge transfer resistance in cathode material. The scanning electron microscopy (SEM) was employed as a morphology indicator of the cathodes.