Tin sulfide (SnS) is a highly promising photovoltaic absorption material in thin-film solar cells with abundant reserves, environmental friendliness, low cost and long-term stability. An efficiency of up to 4.8% has been achieved for SnS absorber/CdS heterojunction solar cells where the CdS buffer layer is usually obtained by chemical bath deposition. However, current CdS/SnS devices often suffer from severe interface recombination loss, which deteriorates device performance. This report focuses on the CdS film surface to identify performance-degrading factors for CdS/SnS-based solar cells. XRD and XPS reveal numerous oxides on freshly fabricated CdS films increasing surface roughness and reducing conductivity. Herein, a method based on ammonium sulfide (AS) chemical treatment is proposed, which can effectively reduce the oxide content on the surface of CdS and optimize the band alignment, leading to the facilitation of charge carrier transport and the suppression of interface recombination. Consequently, the PCE of the FTO/CdS/SnS/Ag device is enhanced about three times (from 0.18% to 0.47%) with excellent moisture stability.