Herein, the extended layer spacing 1T MoSe2 coupled with ZnIn2S4 nanosheets through in-situ growth, and ultimately obtained 1T /2H MoSe2/ZnIn2S4 photocatalysts with S-scheme heterojunction. This rational structure enables photogenerated carriers to rapidly transfer to MoSe2 via Mo-S bond. In order to further address the problem of wasted oxidative half-reaction, we rely on the dehydrogenation of benzyl alcohol as a carrier for hole depletion. Notably, optimized 1T/2H MoSe2/ZnIn2S4 has superior H2 evolution ability, reaching up to 11.271 mmol·g−1·h−1 and the apparent quantum efficiency at 420 nm is 10.3 %. Meanwhile, the conversion rate of benzyl alcohol to high value-added benzaldehyde is 60.60 %. In addition, the Zn acidic sites can achieve polarization of epoxides and precise cleavage C-O bond. Thus, it also has the ability to high selectivity and efficient photocatalytic epoxide alcoholysis. This work proposes a new insight for enhancing photocatalytic properties via regulating IEF to fabricate S-scheme heterostructure.