This study is an attempt to give an account of the preparation of mesoporous TiO2 thick templated films of nonsimilar pore architecture and their use in dye-sensitized solar cells (DSSCs). Highly crystallized mesoporous titania thick templated films with four different morphologies including hexagonal, wormlike, cubic, and gridlike mesostructure, have been successfully synthesized through an evaporation-induced self-assembly (EISA) route followed by layer-by-layer deposition. Stabilization, followed by each coating, and calcinations, carried out after every five layers, were used to produce crack-free thick films. These mesoporous templated titanium dioxide samples were characterized by TEM, XRD, SEM, BET, and UV vis measurements and used as a photoelectrode material in DSSCs. The mesostructured films with a thickness of about 7 mu m demonstrated better performance in comparison to nanocrystalline TiO2 films (NC-TiO2) at a film thickness of 13 mu m as the most typical films utilized in DSSCs. The findings reveal that a surfactant/Ti ratio change undergone for developing cubic mesostructures can enhance the crystallinity and roughness factor and therefore increase the energy conversion efficiency of DSSC. The cell performances derived from these mesofilms were enhanced compared to the efficiencies reported thus far. The best photovoltaic performance of 8.73% came from DSSC using the cubic mesoporous TiO2 photoelectrode with the following properties: open circuit voltage of 743 mV, short circuit photocurrent density of 16.35 mA/cm(2), and fill factor of 0.72.