Major issues in photocatalysis include improving charge carrier separation efficiency at the interface of semiconductor photocatalysts and rationally developing efficient hierarchical heterostructures. Surface continuous growth deposition is used to make hollow Cu S nanoboxes, and then simple hydrothermal reaction is used to make core-shell Cu S@ZnIn S S-scheme heterojunctions. The photothermal and photocatalytic performance of Cu S@ZnIn S is improved. In an experimental hydrogen production test, the Cu S@ZnIn S photocatalyst produces 4653.43 µmol h g of hydrogen, which is 137.6 and 13.8 times higher than pure Cu S and ZnIn S , respectively. Furthermore, the photocatalyst exhibits a high tetracycline degradation efficiency in the water of up to 98.8%. For photocatalytic reactions, the hollow core-shell configuration gives a large specific surface area and more reactive sites. The photocatalytic response range is broadened, infrared light absorption enhanced, the photothermal effect is outstanding, and the photocatalytic process is promoted. Meanwhile, characterizations, degradation studies, active species trapping investigations, energy band structure analysis, and theoretical calculations all reveal that the S-scheme heterojunction can efficiently increase photogenerated carrier separation. This research opens up new possibilities for future S-scheme heterojunction catalyst design and development.