Silanization is an effective approach for the hydrothermal synthesis of hierarchical zeolite. However, the secondary porosity created is subject to the organosilane size. Herein, inert silanes and surfactant were introduced to intensify the interactions between the hydrophobic group of an active organosilane, and hierarchical TS-1 (HTS) with more supermicropores (1-2 nm) and mesopores (2-4 nm) were prepared. More importantly, the modified silanization process is beneficial for titanium incorporation. Consequently, although there is more silicon on the surface of the HTS materials, the accessibility of the active sites located in the inner part of the crystals was improved. In the cyclohexene oxidation and 1-octene epoxidation reactions, enhanced catalytic activity of the HTS catalysts could be achieved, and the increase in the activity was more than 24% when tert-butyl hydroperoxide was the oxidant.