A facile one-pot synthetic strategy is developed to prepare a class of highly crystalline TiO2 materials with uniform mesoporous structure and good thermal stability. The synthesis intricately combines the advantages of the Stöber, surfactant-templated, and hydrothermal methods. The mesopore sizes are well controlled by adjusting the ratio of hydrolysis inhibitor to TiO2 precursor. DSSC testing results highlights the importance of specific surface area and mesopore size to the cell performance. The DSSC based on the optimized mesoporous TiO2 photoanode reached over 8.3 % power conversion efficiency. It is revealed that electron lifetime is greatly increased because of the confinement effect of the uniform mesoporous structure associated with the photoanode. Electron transport is also accelerated as a result of the highly connected crystalline structure for electron transport. Electron diffusion length on the optimized photoanode is about 2.3 times larger than that in a photoanode of Degussa P25 .