After polystyrene@titanium dioxide (PS@TiO2) composite with different size was calcined at designated temperature, TiO2 hollow sphere with controllable size was obtained for high efficient photo-reduction of Cr(VI). The feature of the TiO2 hollow sphere was investigated by SEM, TEM, XRD, UV-Vis, and photoluminescence. The photo-reduction of Cr(VI) were measured for the performance assessment of the TiO2 hollow sphere, Cr(VI) was used as an electron acceptor. After irradiation for 2 h, the photo-reduction rate of Cr(VI) (pH = 2.82) for TiO2(450 nm) was 96%, which exhibited an increase of 5% and 8% compared with TiO2(370 nm) and Ti02(600 nm). The absorption edges of TiO2 hollow sphere (450 nm) was largest with the increasing of hollow sphere size from 370 to 600 nm. The optimal hollow sphere size of TiO2 was 450 nm for the photo-reduction of Cr(VI), because the light-harvesting efficiency (the best of absorption edge) and photo-generated electron-hole separation rate (the best of photo-reduction rate) of TiO2 hollow sphere were controlled by its hollow sphere size. In addition, we find that the behavior of the hydrogen production was inhibited by the coexistence Cr(VI) solution. This study can improve our understanding of the mechanism for the activity enhancement by the optimal hollow sphere size of TiO2. (C) 2016 Elsevier Inc. All rights reserved.