Ti/SiO2 (or Ti/de[B]SiO2) catalysts were prepared by grafting deboronated silica xerogel with gaseous TiCl4. Using TBHP as oxidant, the Ti/de[B]SiO2 catalyst shows both catalytic activity and selectivity in epoxidation of cyclohexene better than 80%, and the activity can be comparable with that of Ti-β. The catalytic activity of Ti/de[B]SiO2 strongly depends on the content of B of support precursor, and the pretreatment temperature of the support. IR studies show that the sites in the deboronated silica xerogel to react with TiCl4 are not only the silanol nests, but also the defect sites produced during the deboronation.