Thin film heterojunction photovoltaic (PV) solar cells play vital role due to its large area, low cost and higher efficiency devices in solar energy conversion. In this work, low-temperature and cost-effective electrodeposition of n-CdSe and p-Cu2Se heterojunction solar cells are developed and explored. The individual part of heterojunction is screened for its structure, morphology, compositional, optical, and photoelectrochemical measurements. Then-CdSe/p-Cu2Se device designed onto an indium-tin-oxide conducting substrate with PEDOT layer sequencing followed gold contact for extracting charge carriers referring to appropriate band energy level diagram elucidate solar-cell type, behavior due easy charge transportation process of holes and electrons in a different direction of heterojunction. Despite a low power conversion efficiency due to weak current density and voltage.