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Sb 2 Se 3 , an emerging promising binary compound semiconductor, was prepared at different substrate temperatures by pulsed laser deposition for thin film solar cells for the first time. In this work, CdS and Sb 2 Se 3 films were subsequently deposited by pulsed laser deposition to simplify the process. Film properties and device performance, closely related to the substrate temperature, were characterized by thermal gravimetric analysis, X-ray diffraction, UV–Vis–NIR spectrophotometer, scanning electron microscope, light and dark current density-voltage, external quantum efficiency and capacitance-voltage, respectively. Results indicate that Sb 2 Se 3 solar cells film deposited at 500 °C is better, with a better efficiency of 3.58%. Furthermore, SnO 2 high resistive layer was introduced into Sb 2 Se 3 solar cell to improve the junction quality, leading to a champion device efficiency of 4.41%. Image 1 • CdS/Sb 2 Se 3 bilayer was deposited by pulsed laser deposition for the first time. • Effects of substrate temperature on film properties and device performance were studied. • Sb 2 Se 3 film deposited at 500 °C is more suitable for Sb 2 Se 3 solar cells. • Champion efficiency of 4.41% was achieved due to the insertion of SnO 2 layer. [ABSTRACT FROM AUTHOR]