Photocatalytic reduction of aqueous Cr(VI) was successfully achieved on nanostructured SnIn(4)S(8). The SnIn(4)S(8) particles with flower-like nanostructure were synthesized via a facile solvothermal method. UV-vis diffuse reflectance spectra (DRS) indicated that the SnIn(4)S(8) particles had strong absorption in visible region and the band gap was estimated to be from 2.27 to 2.35 eV. The photocatalytic reduction of aqueous Cr(VI) by flower-like SnIn(4)S(8) was evaluated under visible light (λ>400 nm) irradiation. The polyvinyl pyrrolidone (PVP) assisted SnIn(4)S(8) sample exhibits excellent removal efficiency of Cr(VI) (~97%) and good photocatalytic stability. The predominant photocatalytic activity is due to its large surface area, strong absorption in visible-light region and excellent charge separation characteristics.