The macro porous TiO2 applied as the electrode materials were prepared by a matrix-assisted method in this study. The matrix for the preparation of the macro porous materials was used polystyrene nano spheres. The precursor for a preparation of TiO2 was used TiCl4. The morphology of TiO2 synthesized by a matrix-assisted method was the macro-porous material of the ordered type. In this study, the ordered type macro-porous TiO2 layer as the solid oxide electrode was formed over FTO glass for high efficient DSSCs. TiO2 synthesized in this study was applied as the electrode for dye sensitized solar cells (DSSCs). The cell efficiency of DSSCs with the macro-porous TiO2 was investigated and the cell efficiency was enhanced with increasing density of macro pores. These results were concluded, because the shadow effect of the macro porous materials under photo radiation decreased.