In this study, visible-light-active iron tungstosilicate (FeSiW) was fabricated via solvothermal method. Fe3+ was applied as counter ion to precipitate with silicotungstic acid (H4SiW12O40) in methanol solution. It can be observed from FT-IR spectra that the Keggin structure of SiW12O404- was well maintained in FeSiW. Besides, the effect of different initial molar ratios of Fe3+ to H4SiW12O40 was investigated (from 4:1 to 4:4). By photoelectrochemical characterizations, such as photocurrent response and Mott-Schottky (M-S) plots, easiest generation of electron-hole pairs and lowest charge transfer resistance can be observed on FeSiW with initial molar ratio of 4:3. Moreover, FeSiW with 4:3 ratio also displayed highest activity for photocatalytic reduction of Cr(VI), despite of the largest band gap (ca. 2.71 eV). The lowest unoccupied molecular orbital (LUMO) and highest occupied molecular orbital (HOMO) of the optimized FeSiW were estimated to be +0.03 V and 2.74 V vs NHE, respectively, which were thermodynamically feasible for Cr(VI) reduction and H2O oxidation. Even under acidic condition (pH 3), the optimized photocatalyst displayed good stability in cyclic runs. Therefore, the present study opens a new way for heterogeneous polyoxometalates as efficient photocatalyst for environmental application. (C) 2019 Elsevier Inc. All rights reserved.