Well-designed heterojunction semicounductor coupled with high-conductive cocatalyst can obtain boosted photocatalytic activity. Herein, a novel three-dimensional (3D) hollow heterojunction was prepared by coating the indium zinc sulfide (ZnIn2S4) nanosheets with rich-zinc vacancies (VZn) on 3D hollow titanium carbide (Ti3C2). The obtained 3D hollow heterojunction (Ti3C2@ZnIn2S4) achieved effective optical collection and promoted the separation and transmission of photogenerated carriers as well as the surface reaction of spatial separation. In addition, time-resolved photoluminescence and steady-state photoluminescence spectra indicated that the existence of VZn and the introduction of hollow Ti3C2 spherical shell effectively inhibited the recombination of photogenerated carriers and accelerated their separation and transmission, thus further enhancing the photocatalytic activity. In addition, the introduction of 3D hollow Ti3C2 benefited a larger specific surface area for heavy metal adsorption. Due to the unique structural and compositional characteristics, the heterojunction showed high efficiency of Cr(VI) reduction under visible light. In particular, the optimal Ti3C2@ZnIn2S4 heterojunction (1%-Ti3C2@ZnIn2S4) achieved 100% removal of Cr(VI) within 25 min, with a reaction rate constant of 0.225, which was 8.5 times higher than that of the pristine ZnIn2S4. The superior reusability and structural stability further indicated the MXene-based novel photocatalyst is promising for application in environmental remediation.