Since the conversion efficiency of silicon (Si)-based solar cells stagnates at 26.7% in the literature, extensive research and development activities are carried out on perovskite silicon-based tandem solar cells. However, the presence of lead (Pb) and the instability of perovskite prevent their large-scale implementation in the photovoltaic industry. Therefore, it is important to replace the hazardous material (Pb) in perovskite top cells to design non-toxic perovskite–silicon tandem solar cells. The current work yields much-needed studies to develop a non-toxic perovskite–silicon-based tandem solar cell. For the first time, methylammonium tin mixed halide (MASnI3–xBrx)-based materials are comprehensively investigated and optimized with respect to different halide compositions, absorber layer thickness, and bulk defect density in standalone configurations, followed by the development of a lead-free MASnI2Br1–Si-based tandem solar cell. The transfer matrix method and current matching techniques are used to design the two-terminal monolithic tandem cell, which showed a maximum conversion efficiency of 30.7% with an open circuit voltage (VOC) of 2.14 V. The results outlined in this manuscript will pave the way for the progress of highly efficient, non-toxic perovskite–silicon tandem solar cells.