The　construction　of　NiTiO3/Cd0.5Zn0.5S　heterostructures　is　presented　as　all-solid-state　direct　Z-scheme　photocatalysts　for　the　efficient　and　stable　hydrogen　production　under　visible　light.　The　NiTiO3/Cd0.5Zn0.5S　hybrids　are　assembled　by　growing　Cd0.5Zn0.5S　nanoparticles　on　the　surface　of　NiTiO3nanorodsviaa　co-precipitation　and　hydrothermal　coupled　method.　The　compositional　and　structural　features　of　the　NiTiO3/Cd0.5Zn0.5S　composites　are　fully　disclosedviadiverse　physicochemical　characterizations.　The　NiTiO3/Cd0.5Zn0.5S　heterostructures　are　revealed　to　effectively　capture　the　optical　spectrum　in　the　visible　region　as　well　as　enhance　the　transfer　and　separation　of　photogenerated　charge　carriers　through　the　Z-schematic　pathway.　Consequently,　the　optimized　NiTiO3/Cd0.5Zn0.5S　photocatalyst　shows　a　high　H2production　rate　of　1058　μmol　h−1(26.45　mmol　h−1g−1),　which　is　independent　of　any　cocatalysts　(such　as　Pt),　together　with　a　high　apparent　quantum　yield　(AQY)　of　34%　under　monochromatic　light　irradiation　at　420　nm.　Besides,　the　NiTiO3/Cd0.5Zn0.5S　composites　also　exhibit　a　high　stability　for　the　H2evolution　photocatalysis　mainly　due　to　the　fact　that　the　Z-schematic　charge　separation　and　migration　can　enable　the　efficient　consumption　of　light-induced　holes　of　Cd0.5Zn0.5S　to　prevent　the　photocorrosion　effect.　Finally,　a　possible　photocatalytic　H2evolution　mechanism　over　the　Z-schematic　NiTiO3/Cd0.5Zn0.5S　heterostructures　is　also　presented　based　on　the　results　of　the　band　structures,　density　functional　theory　(DFT)　calculations　and　electron　spin　resonance　(ESR)　tests.　©　The　Royal　Society　of　Chemistry　2021.