AbstractA two‐compartment electrochemical photocell using nickel‐based polycrystalline CdSe, CdS, and mixed chalcogenides showed promising potential for constructing regenerative and/or storage batteries. The cell was able to generate photovoltages of up to 700 mV and photocurrent of 2–6 mA/cm2when different aqueous electrolytes were used in the dark compartment. The illuminated compartment was filled with polysulphide electrolyte and light intensity used was 70 mW/cm2. Properties such as the open‐circuit voltage, the short‐circuit current, the efficiency, and the effect of applied voltages in different redox couples are