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Ordered porous TiO 2 thin films were fabricated on conductive glass by using colloid crystal template of polystyrene (PS) spheres. Microstructural characterization by scanning electron microscopy techniques was carried out to explore the porous structural changes due to the PS templates which could be controlled by adjusting the drawing rate. Photovoltaic performance was measured and this revealed the effect of microstructural changes. The results showed that monolayer porous TiO 2 films and multilayer porous TiO 2 films could be successfully prepared. And multilayer porous TiO 2 films provided large surface area for dye absorption to increase the efficiency of dye-sensitized solar cells (DSSCs) which were assembled by porous TiO 2 films.