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Photocatalytic reduction of CO2 is increasingly attracting research interest for the growing concerns about climate change resulted from the greenhouse effect due to the industrial emission of CO2. In this paper, we report the synthesis of Zn3In2S6 modified TiO2 nanocomposite via a facial hydrothermal method. The samples were characterized by photoluminescence spectra (PL), UV-vis diffuse reflectance spectra (DRS), X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscope (TEM), X-ray photoelectron spectroscopy (XPS) and energy dispersive X-ray spectroscopy (EDS). The production rate of CO from CO2 is dramatically improved over the obtained composite catalyst. The contact between Zn3In2S6 and TiO2 is responsible for this ameliorated photocatalytic activity because of the formation of the Z-scheme charge transfer mechanism which favors the separation of photo-induced charges.