In this study, Cd1-xZnxSySe1-y (0 <= x = y <= 0.35) photoelectrodes are deposited via inexpensive facile chemical bath deposition. The effects of Zn and S doping on the compositional, microstructural, electrical, and optical properties of thin films were analysed. The electrochemical photovoltaic (EPV) cell of configuration Cd1-xZnxSySe1-y/0.25M sulfide/polysulfide/C was assembled to examine the different performance parameters in light and in dark conditions. An EPV cell fabricated with the Cd1-xZnxSySe1-y (0 <= x = y <= 0.075) photoelectrode exhibited a maximum photoconversion efficiency of 3.18%. This performance can be attributed primarily to the enhanced light-absorption ability of the material because of the enhanced rough microstructure and low recombination of photo-injected electrons with the electrolyte. The photovoltaic (PV) performance is significantly enhanced after doping CdSe with Zn and S.