The increasing environmental pollution and looming energy crisis necessitate the development of advanced photocatalysts that demonstrate efficient separation and transfer of the photo-generated holes and electrons, as well as multiple functions to address the above issues. Herein, a bifunctional Ni3S4/NiS2/v-Zn3In2S6 photocatalyst has been constructed to degrade environmental hormones and antibiotics with simultaneous H2 production. Sulfur vacancies have been engineered in the Zn3In2S6 from a kinetic point of view to accelerate the separation of photogenerated charge carriers and act as active sites. Ni3S4 and NiS2 are introduced to construct cascade electric fields with Zn3In2S6 via ohmic junctions for spatially separated charge carriers and reduced hydrogen evolution potential. As a result, the composite exhibits enhanced photocatalytic H2 production and efficient degradation of bisphenol A, norfloxacin, and tetracycline, respectively. Specifically, the degradation pathways of BPA have been investigated based on Fukui calculations and liquid chromatography-mass spectrometry techniques. This work may shed new light on the design and construction of dual-function photocatalysts for wastewater treatment and H2 production.