Synthesis and characterization of undoped and samarium-doped CuO–SnO₂:F thin films using the spray pyrolysis technique are presented. The effect of the samarium doping level on the physical properties of these films was thoroughly analyzed. X-ray diffraction patterns proved the successful synthesis of pure CuO–SnO₂:F thin films, free from detectable impurities. The smallest crystallite size was observed in 6% Sm-doped CuO–SnO₂:F thin films. The 6% Sm-doped CuO–SnO₂films demonstrated an increasedsurface area of 40.6 m²/g, highlighting improved textural properties, which was further validated by XPS analysis.The bandgap energy was found to increase from 1.90 eV for undoped CuO–SnO₂:F to 2.52 eV for 4% Sm-doped CuO–SnO₂:F, before decreasing to 2.03 eV for 6% Sm-doped CuO–SnO2:F thin films. Photoluminescence spectra revealed various emission peaks, suggesting a quenching effect. A numerical simulation of a new solar cell based on FTO/ZnO/Sm–CuO–SnO₂:F/X/Mo was carried out using Silvaco Atlas software, where X represented the absorber layer CIGS, CdTe, and CZTS. The results showed that the solar cell with CIGS as the absorber layer achieved the highest efficiency of 15.98. Additionally, the thin films demonstrated strong photocatalytic performance, with 6% Sm-doped CuO–SnO₂:F showing 86% degradation of ampicillin after two hours. This comprehensive investigation provided valuable insights into the synthesis, properties, and potential applications of Sm-doped CuO–SnO₂ thin films, particularly for solar energy and pharmaceutical applications.