Four small molecule (DRTTBDT-A1 to DRTTBDT-A4) based on Benzodithiophene were studied for their optoelectronic properties and compared to the reference molecule (DRTTBDT-R) as potential donors in organic solar cells. The designed molecules feature electron-withdrawing moieties attached to both terminals of the reference molecule. Computational investigations using density functional theory indicated that DRTTBDT-A1 displayed the most intriguing characteristics in dichloromethane solvent, with a small energy gap of 3.84 eV, a high λmax at 519 nm, and a large dipole moment of 5.92 D. These features suggest superior miscibility and potential for high performance in OSCs. The newly engineered molecules also exhibited higher open-circuit voltage and power conversion efficiency compared to the reference, indicating enhanced operational efficiency. PCE values ranging from 27.90 to 31.71 were observed, surpassing the reference molecule's PCE of 27.49. These findings demonstrate the potential of structural modifications in designing efficient photovoltaic materials for solar energy applications.