The effect of the Gd/Sn composition ratio of Cu2Sn1-xGdxS3 is examined. The films are fabricated on glass substrates in a sulfur atmosphere via the spin coating. The influence of the Gd/Sn composition ratio on the structural, morphological, optical, and electrical properties of the films is investigated using X-ray diffraction, FESEM, UV-Vis, and Hall effect. XRD patterns for the films revealed that all films have a monoclinic polycrystalline. The morphological and optical properties of the films show the formation of spherical grains and polygonal structures with an energy band in the range of 2.10–1.50 eV. The electrical properties of the films are changed by increasing the Gd/Sn composition ratio in the film. Furthermore, the Cu2Sn1-xGdxS3/CdS heterojunction solar cell was modeled by SCAPS-1D. The optimized conditions yielded exceptional photovoltaic parameters, achieving an open-circuit voltage of 0.7885 V, short circuit current density of 41.09 mA/cm2, fill factor of 85.30%, and an efficiency of 27.3%.