Abstract: The present invention provides a catalyst and the preparation process thereof and a process of epoxidising olefin using the catalyst. The catalyst contains a binder and a titanium silicate, the binder being an amorphous silica, the titanium silicate having a MFI structure, and the crystal grain of the titanium silicate having a hollow structure, with a radial length of 5-300 nm for the cavity portion of the hollow structure, wherein the adsorption capacity of benzene measured for the titanium silicate under the conditions of 25 degrees C., P/P0=0.