Electrochemical behavior of zinc and thin polyaniline (PANI) electrodes in citrate/chloride-contained electrolyte has been investigated by the means of electrolyte composition optimization. Electrolyte contained 0.8 M sodium citrate, 0.3 M ammonium chloride, and ~0.3 M zinc chloride has been found to be an optimum electrolyte for the further applications in the real zinc–polyaniline citrate/chloride-based secondary cell.