Here, we are presenting the effect of electron irradiation on the solar cell properties of Cd_0.3Zn_0.7S electrodes. Briefly, Cd_0.3Zn_0.7S thin films have been synthesized by an electrodeposition method which is further characterized by different physiochemical techniques. Our results revealed the formation of Cd_0.3Zn_0.7S thin films with significant morphological deviation through deposition potential. Moreover, considerable positive effect of deposition potential on the electrochemical irradiation of Cd 0.3 Zn 0.7 S electrodes has been witnessed. Later,the results suggest that Cd_0.3Zn_0.7S electrode irradiated at potential 25 kGy with nanoparticle like nanostructures exhibited. Further photovoltaic activity of films was studied by forming the photoelectrochemical cell having Cd_0.3Zn_0.7S/0.5 M (Na₂SO₃)/C cell configuration. The maximum efficiency and fill factor of these PEC cells are found to be 1.40% and 0.68%, respectively.