The present paper focuses on the properties of the p–Si/ ZnSxSe1−x (0 ≤ x ≤ 1) heterojunctions in photodetector applications. The heterostructures were fabricated by depositing ZnSSe on Si wafer using the thermal co-evaporation technique with ZnS and ZnSe powders. The GIXRD study showed that films were in cubic phase, and the prominent peak was shifted with composition x. The maximum crystallite size of the films was found for x = 0.8. The presence of point defects and emission related to higher Zn content in the thin films was confirmed by Photoluminescence. Temperature-dependent Raman analysis reveals that the longitudinal optical phonon modes shift to the lower wavenumber side as temperature decreases, which describes the variation of lattice parameters with temperature. The barrier height and ideality factor were calculated by implementing the thermionic emission. The photoresponse of p–Si/ ZnSxSe1−x heterostructures was studied. The investigation showed that the sample with x = 0.8 exhibits high photosensitivity and is suitable for photodetector applications.