CuSbS2 (Chalcostibite) crystals were synthesized by the hot-injection method as triangular and spherical shaped structures. The crystals were inserted by spin coating technique as interfacial layers between Au metal and p-Si to investigate their electrical and photoresponse properties via I-V measurements under various light intensities. The XRD measurements were performed to show the crystalline structure of the spherical and triangular CuSbS2. The TEM images confirmed the triangular and spherical particle structures of the CuSbS2 crystals. The I-V measurements were performed under dark, 20–100 mW light intensities with 20 mW interval for spherical and triangular CuSbS2 photodiodes. In addition, diode parameters were extracted and discussed in the details. The results highlighted that triangular and spherical shaped structures have good photoresponse to the illumination and can be employed in the photodiode and photodetector applications.