Facile and effective approaches were developed to fabricate the inverse TiO2/Pt opals Schottky structures on the Ti substrate. The as-prepared samples were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), and diffuse reflectance UV-vis spectra (DRS), respectively. The results indicate that these samples were of ordered network, which was built by the Pt skeleton frame and the outer TiO2 layer. The TiO2 layer was identified as anatase with the preferential orientation of (101) plane. The experiments of short-circuit photocurrent (SCPC) and photocatalytic degradation of phenol were also conducted under the UV irradiation in order to evaluate the photoactivity of the samples. By tuning the red edge of photonic stop-band overlapping the absorption maximum of anatase (at 360 nm), both the UV absorption and the carrier separation of the samples were improved. The kinetic constant using the optimal inverse TiO2/Pt opals (0.992 h(-1)) was about 1.5 times as great as that of the disordered inverse TiO2/Pt opals (TiO2/Pt-mix) and was 3.3 times as great as that of pristine TiO2 nanocrystalline film (TiO2-nc) on Ti substrate.