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In this work, a numerical assessment of the optoelectrical properties of the ZnO–ZnSe–CdSe heterojunction for a thin and cost-effective solar cell was made by using the PC1D simulation software. The photovoltaic (PV) properties have been optimized by varying thicknesses of the absorber layer of the p-CdSe layer, the window layer of n-ZnSe, and the antireflection coating (ARC) layer of ZnO, a transparent conductive oxide with enhanced light trapping, and wide bandgap engineering. There is a positive conduction band offset (CBO) of ΔEc = 0.25 eV and a negative valence band offset (VBO) of ΔEv = 1.2 − 2.16 = − 0.96 eV. The positive CBO prevents the flow of electrons from the CdSe to the ZnSe layer. Further, the impact of doping concentration on the performance of solar cells has been analyzed. The simulation results reveal the increase in the efficiency of solar cells by adding an ARC. The rapid and sharp increase in the efficiency with the thickness of the window layer beyond 80 nm is interesting, unusual, and unconventional due to the combined effect of morphology and electronics on a macro-to-micro scale. The thin-film solar cell with the structure of ZnO/ZnSe/CdSe exhibited a high efficiency of 11.98% with short-circuit current (Isc) = 1.72 A, open-circuit voltage (Voc) = 0.81 V and fill factor (FF) = 90.8% at an optimized thickness of 2 μm absorber layer, 50 nm window layer, and 78 nm ARC layer. The EQE of solar cells has been observed at about 90% at a particular wavelength at 470 nm (visible light range). Around 12% of efficiency from such a thin-layered solar cell is highly applicable.