Ti containing wrinkled mesoporous silica (Ti-WMS) has been prepared by direct synthesis with various Si/Ti ratios. Under similar conditions, Ti containing periodic mesoporous organosilicas (Ti-PMO) has been prepared with benzene bridges in the framework while maintaining the wrinkled structure. Both Ti-WMS and Ti-PMO samples have the radial wrinkled structure, and were further modified by trimethylsilylation to adjust the surface hydrophobicity. All catalysts were tested for the oxidation of cyclohexene with and without solvent using tert-butyl hydroperoxide as the oxidant. Ti-WMS catalysts showed superior catalytic performance over conventional Ti-MCM-41 when acetonitrile was used as the solvent. The radial wrinkled structure ensures better diffusion pathways for the reactants. For the catalytic reaction without solvent, Ti-WMS catalysts exhibit similar behavior to the conventional Ti-MCM-41 catalyst. Silylation was demonstrated to be an effective methodology to improve the catalytic activity because of enhanced surface hydrophobicity. The maximum turnover frequency was 1401 h−1 with an epoxide selectivity of 95% obtained using the silylated Ti-WMS catalyst with a Si/Ti ratio of 209.