Strategies for improving the photovoltaic performance of dye-sensitized solar cells (DSSCs) are proposed by modifying highly transparent and highly ordered multilayer mesoporous TiO2 photoanodes through nitrogen-doping and top-coating with a light-scattering layer. The mesoporous TiO2 photoanodes were fabricated by an evaporation-induced self-assembly method. In regard to the modification methods, the light-scattering layer as a top-coating was proved to be superior to nitrogen-doping in enhancing not only the power conversion efficiency but also the fill factor of DSSCs. The optimized bifunctional photoanode consisted of a 30-layer mesoporous TiO2 thin film (4.15 mm) and a Degussa P25 light-scattering top-layer (4 mm), which gives rise to a similar to 200% higher cell efficiency than for unmodified cells and a fill factor of 0.72. These advantages are attributed to its higher dye adsorption, better light scattering, and faster photon-electron transport. Such a photoanode configuration provides an efficient way to enhance the energy conversion efficiency of DSSCs.