The concept of bi-layer structure in photoanodes is of great importance to prepare highly efficient dye-sensitized solar cells. In this work, Hollow TiO2 (H-TiO2) NPs are successfully produced through the etching of Au NPs in Au@TiO2 core-shell NPs which were synthesized by microwave hydrothermal route. Electrophoretic deposition was utilized to make H-TiO2 NP scattering layer on the top of small sized TiO2 NPs layer. The photoanodes based on H-TiO2 NPs scattering layer showed a photoconversion efficiency of 7.58% which is much higher than that of photoanode without H-TiO2 scattering layer (6.08%). The improved photovoltaic performance is mainly due to relatively light scattering effect, more surface area for effective dye adsorption and increased light harvesting capacity of H-TiO2 NPs in the entire spectral range.