A novel three dimensionally ordered macroporous (3DOM) Ti3+ self-doped TiO2 with an ordered distribution of macropores in the diameter of 270 nm is synthesized by a facile colloidal polystyrene template sol-gel and ice-water quenching method. The performance of photocatalytic removal of NO from continuous air flow with visible light irradiation show 3DOM Ti3+ self-doped TiO2 has enhanced efficiency under visible light irradiation. The improved photocatalytic efficiency could contribute to the presence of Ti3+ doping induced by ice-water quenching and the 3DOM structure with a large specific surface area.