A hierarchical titanium silicate (TS-1) that possesses large open voids has been prepared by using a dissolution/re-crystallization process. Carbon black was introduced as a hard template during the synthesis process to generate defects both inside and on the surface of crystals, then TPAOH post-treatment was applied, as a result, a novel TS-1 zeolite crystal with large open voids was successfully synthesized. The synthesized hierarchical TS-1 was characterized by XRD, FTIR, SEM, TEM and N 2 physisorption. Compared with the traditional TS-1 and hollow TS-1, the activity of hierarchical TS-1 in cyclohexanone ammoximation was improved and attributed to the macropores that linked the voids inside the zeolite directly to the outer surface.