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Constructing appropriate heterojunction systems has been considered the most promising among different methods for achieving effective charge transfer and separation to improve photocatalytic performance. Herein, SnS2/g-C3N4 composites consisting of SnS2 nanosheets loaded on a porous g-C3N4 matrix were successfully prepared via direct calcination from the precursors of tin (IV) chloride and thiourea. Under visible light, all the composites outperformed pure SnS2 and g-C3N4 in terms of Rhodamine B (RhB) photodegradation, and the highest removal efficiency after 6 h of irradiation was 92.22%. Their photocatalytic performance was significantly enhanced because of the positive synergistic relationship between semiconductors (SnS2 and g-C3N4) and the rational Step-scheme charge transfer mechanism. Thus, these composites contributed to the strong redox power, high migration efficiency, and extended lifetime of photogenerated carriers.