Nanocrystalline mesoporous TiO 2 -based catalysts prepared by a surfactant-assisted templating sol–gel process were tested on epoxidation of cyclohexene in tert-butanol–H 2 O 2 system. The mesoporous TiO 2 showed exceptional potential for epoxidation of cyclohexene, exhibiting both higher cyclohexene conversion and higher cyclohexene oxide selectivity than non-mesoporous commercial TiO 2 powders, i.e. Ishihara ST-01 and Degussa P-25. The oxides of Fe, Co, Ni, and Ru were also loaded by incipient wetness impregnation method onto the synthesized mesoporous TiO 2 , aiming to enhance the catalytic performance. Among metal oxide-loaded catalysts, RuO 2 -loaded mesoporous TiO 2 was proved to possess noticeably high catalytic performance based on cyclohexene oxide selectivity. The 1mol% RuO 2 -loaded mesoporous TiO 2 was the best catalyst, showing the highest cyclohexene oxide selectivity and lowest cyclohex-2-en-1-ol (undesired product) selectivity. Plausible reaction pathways were also proposed.