Hierarchically macro-/mesoporous Ti-Si oxides photonic crystal (i-Ti-Si PC) with highly efficient photocatalytic activity has been synthesized by combining colloidal crystal template and amphiphilic triblock copolymer. It was found that the thermal stability of mesoporous structures in the composite matrix were improved due to the introduction of silica acting as glue and linking anatase nanoparticles together, and the photocatalytic activity of the i-Ti-Si PCs was affected by the calcination conditions. The influences of photonic and structural effect of the i-Ti-Si PCs on photocatalytic activity were investigated. Photodegradation efficiency of the i-Ti-Si PCs was 2.1 times higher than that of TiO(2) photonic crystals (i-TiO(2) PCs) in the photodegradation of Rhodamine B (RB) dye as a result of higher surface area. When the energy of slow photon (SP) was optimized to the abosorption region of TiO(2), a maximum enhanced factor of 15.6 was achieved in comparison to nanocrystalline TiO(2) films (nc-TiO(2)), which originated from the synergetic effect of SP enhancement and high surface area.