<p>The inorganic perovskite Ba₃SbI₃ has recently attracted attention as a promising photovoltaic absorber due to its strong optical absorption, favorable electrical conductivity, structural stability, and compositional tunability. In this work, the photovoltaic potential of Ba₃SbI₃ is systematically investigated using the SCAPS-1D simulator. Twelve perovskite solar cell (PSC) architectures were designed by integrating seven novel charge transport layer (CTL) materials to identify the most efficient configuration. The absorption coefficient and bandgap of Ba₃SbI₃, obtained from theoretical calculations and reported literature, were used as key input parameters for device modeling. Each architecture exhibited distinct optimized parameters and performance, influenced by electric field distribution, band offsets, and interface alignments. To further enhance the power conversion efficiency (PCE), the thicknesses of both the absorber and CTLs were optimized, alongside improvements from a back-reflection layer and tailored electrode work functions. The optimal device structure, FTO/n-Si/ Ba₃SbI₃/CuI/Pt achieved a maximum PCE of 26.38%, with a short-circuit current density of 44.16&#xa0;mA cm⁻², an open-circuit voltage of 0.71&#xa0;V, and a fill factor of 84%. This superior performance results from efficient charge extraction and reduced recombination losses enabled by optimized CTLs. These findings underscore the critical role of CTL engineering and structural optimization in advancing Ba₃SbI₃-based PSCs and provide practical guidance for their experimental realization.</p>