As the demand of fossil fuels continues to expand, hydrogen energy is considered a promising alternative energy. In this work, the NiTiO<sub>3</sub>-CuI-GD ternary system was successfully constructed based on morphology modulation and energy band structure design. First, the one-pot method was used to cleverly embed the cubes CuI in the stacked graphdiyne (GD) to prepare the hybrid CuI-GD, and CuI-GD was anchored on the surface of NiTiO<sub>3</sub> by simple physical stirring. The unique spatial arrangement of the composite catalyst was utilized to improve the hydrogen production activity under light. Second, to combine various characterization tools and energy band structures, we proposed an step-scheme (S-scheme) heterojunction photocatalytic reaction mechanism, among them, the tubular NiTiO<sub>3</sub> formed by the self-assembled of nanoparticles provided sufficient sites for the anchoring of CuI-GD, and the thin layer GD acted as an electron acceptor to capture a large number of electrons with the help of the conjugated carbon network; cubes CuI could consume holes in the reaction system; the loading of CuI-GD greatly improved the oxidation and reduction ability of the whole catalytic system. The S-scheme heterojunction accelerated the transfer of carriers and improved the separation efficiency. The experiment provides a new insight into the construction of an efficient and eco-friendly multicatalytic system.