This paper presents detailed results regarding the physical behavior of Cs₂SnI_6−xBr_x alloys for their potential use in photovoltaic applications. Numerical computations based on density functional theory (DFT) revealed that Br substitution at I sites significantly influenced the electronic structure of Cs₂SnI₆, resulting in an increase in bandgap values from 1.33 eV to 2.24 eV. Additionally, we analyzed the optical properties, including the absorption coefficient, which exhibited high values in the visible light region, highlighting the material’s excellent light-trapping abilities. Moreover, Cs₂SnI_6−xBr_x compounds were employed as absorber materials in an fluorine-doped tin oxide (FTO) TiO₂/Cs₂SnI₆/P3HT/Ag perovskite solar cell (PSC) to investigate its performance. The simulation process consisted of two interconnected steps: (i) the DFT calculations to derive the material properties and (ii) the SCAPS–1D (one-dimensional (1D) solar cell capacity simulator) simulation to model device performance. To ensure reliability, the SCAPS–1D simulation was calibrated against experimental data. Following this, Cs₂SnI_6−xBr_x compound with various ratios of Br content, ranging from 0 to 6, was investigated to propose an efficient solar cell design. Furthermore, the cell structure was optimized, resulting in a development in the power conversion efficiency (PCE) from 0.47% to 3.07%.