Cu2ZnSnS4 (CZTS) hierarchical microstructures were synthesized by using a facile and nontoxic hydrothermal route, which were characterized by X-ray powder diffraction (XRD), scanning electron microscope (SEM), Raman spectra, and UV–Vis absorption spectra. The results and analysis show that surfactants used in the hydrothermal process have significant effect on the phase structures, morphologies, and photocatalytic activities of CZTS powders. Especially, the well-crystallized and pure kesterite CZTS hierarchical microstructures were synthesized with the addition of high-concentration tartaric acid (TA) in the hydrothermal process. A nucleation–dissolution–recrystallization mechanism was discussed, and the photocatalytic activities of CZTS hierarchical microstructures for the degradation of rhodamine B (RhB) were also evaluated. We argue that the crystalline structure and particle morphology have played key roles on the photocatalytic properties of CZTS crystals. A considerably high photocatalytic efficiency of 51.66% after 4 h irradiation was obtained in pure kesterite CZTS hierarchical microstructures, which suggests that CZTS would be a promising candidate of photocatalyst.