Herein, a new heterojunction photovoltaic (PV) device is designed by incorporating molybdenum trioxide (MoO3) as a hole transport layer (HTL), tin sulfide (SnS) as an absorber, and tungsten disulfide (WS2) as an electron transport layer (ETL). The PV outputs of the proposed thin‐film solar cell (TFSC) of Ni/MoO3/SnS/WS2/FTO/Al are investigated using the widely used solar cell simulator (SCAPS‐1D). It is found that the SnS TFSC with suitable band alignments at both the SnS/WS2 and MoO3/SnS interfaces gives better photoconversion efficiency than the conventional one. To optimize the material properties, the performance parameters, including open‐circuit voltage (Voc), short‐circuit current density (Jsc), fill factor (FF), and efficiency, have been calculated by varying the influences of the material's thickness, doping concentration, bulk and interface defect densities, operational temperature, and work function of back‐contact. At optimized thicknesses of 0.1 μm for MoO3 HTL and 1.0 μm for SnS absorber, the efficiency is estimated to be 30.42% with Voc of 1.02 V, Jsc of 34.38 mA cm−2, and FF of 87.04% for the suggested TFSC. These outcomes imply that the nontoxic MoO3 and WS2 materials can be applied as HTL and ETL into the inexpensive, highly efficient, and environmentally friendly SnS‐based PV cell.