A range of TiO2 inverse opals with tunable macroporous size were synthesized using different sized PS (polystyrene sphere) arrays as hard templates. After a simple heating treatment in vacuum, Ti3+ doped TiO2 inverse opals were obtained. The materials were characterized and verified by XRD, XPS, UV-vis DRS, EPR, and SEM. The result indicated that the optical responses of TiO2 and Ti3+ doped TiO2 inverse opals could be enhanced by choosing PS arrays with appropriate size as hard templates due to the slow light effect of inverse opal structure. The photocatalytic efficiency was evaluated by the photo degradation of AO7, and it is proved that the cooperation of slow light effect and Ti3+ doping is an effective way to improve visible-light driven photocatalytic performance of TiO2 photocatalyst. (C) 2014 Elsevier B.V. All rights reserved.