The physical, chemical, and electrical properties of materials are influenced by the shape, size, and surface morphology such as rod, core-shell, network, and flowers. Herein, hollow nano-belt SnS/NiS composite structure was synthesized by the high-temperature wet chemical method in the presence of as-synthesized SnS as seed, and its photoresponse was evaluated by fabricating P-N junction photodiode using n-type Si substrate. Phases that are presented in the synthesized samples were characterized by powder diffraction method. Morphology of SnS and hollow nano-belt formation in SnS/NiS was confirmed by transmission electron microscopy. The solution-processed photodiode was fabricated using synthesized p-type SnS and SnS/NiS on n-Si substrate, and photoresponse was compared with each other. Observed photodiode results revealed that hollow nano-belt based p-SnS/NiS/n-Si photodiode has better photoresponsivity 98.95 mA/W than photodiode fabricated using bare SnS sample. Also, its photosensitivity (275.989% at 3 V), EQE (38.371%), and D* (2.0080 × 1010 Jones) are noticed to be higher when compared with p-SnS/n-Si diode. The enhanced values of fabricated diode make it suitable for high photodetection applications.