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Due to the exceptional potential to retard the charge recombination, semiconductor-based heterojunctions as photocatalysts have attracted extensive attention. Herein, nickel(II) 5,10,15,20-tetraphenyl-21H,23H-porphyrin (NiTPP) and ZnIn 2 S 4 (ZIS) floriated microspheres are used to construct a novel inorganic-organic heterojunction (NiTPP/ZIS). Compared with the NiTPP and ZIS, the resultant NiTPP/ZIS exhibits enhanced optical absorption, charge separation and photoelectrochemical behavior. Further investigations demonstrate that a type II heterojunction mechanism proceeds in the NiTPP/ZIS heterojunction to boost the charge separation via the Ni-S highway formed between the NiTPP and ZIS components. No need of additional cocatalyst, the NiTPP/ZIS heterojunction with an optimal mass ratio delivers a superior apparent quantum yield of 64.0% at 400 nm and a remarkable H 2 evolution activity of 2305 μmol h−1 under visible light (λ ≥ 400 nm) irradiation, 10 and 256 times higher than that of the ZIS and NiTPP alone, respectively. This work presents a new concept for constructing inorganic-organic heterojunctions for high-performance artificial photosynthesis systems. [Display omitted] • A novel NiTPP/ZIS inorganic-organic hybrid material is synthesized via reflux method. • Ni-S channel between the NiTPP and ZIS components acts as highway for charge transfer. • A type II heterojunction mechanism is promoted via the Ni-S charge transfer channel. • Efficient charge separation causes superior apparent quantum yield of 64.0% at 400 nm. • Achieved 10 times higher H 2 yield than ZIS irradiated by visible light without cocatalyst. [ABSTRACT FROM AUTHOR]