Nanocrystalline titanium dioxide (TiO₂) materials have been widely used as an electron collector in DSSC. In TiO₂ electrode structures, their geometrical structures and crystalline phase have been extensively investigated as important issues. In this study, we present a new strategy to fabricate a photoelectrode having a periodic structured TiO₂ film templated from 2D or 3D polystyrene(PS) colloid array(CA). One is the igloo-shaped electrode prepared by TiO₂ deposition by RF-sputtering onto 2D CA. The existence of voids at the interface between the film and substrate might be expected to play the predominant roles as scattering spherical voids to promote a light harvesting effect, a spacious structure for electrolytes with higher viscosity and effective paths for electron transfer. Additionally TiO₂ phase prepared by RF-sputtering method was previously reported to improve the electron drift mobility. This yields solar cells with a cell efficiency of 2.45 % or more at AM 1.5 illumination and at the thickness of 2 μm. The other is the inverse opal photonic crystal electrode prepared by titania particles infusion within 3D CA. To obtain the enlargement of ordered area and high quality of crystallinity, the synthesis of titania particles coated with a organic thin layer were applied and well dispersed. This ordered mesoporous structure provides the large surface area and have an light harvesting effect due to the photonic band gap properties. These materials may have promising potentials for future applications of membrane, sensor and so on as well as solar cells.