Silsesquioxanes containing tetrapodal titanium species and alkenylsilyl groups were immobilized onto dimethylsilyl-functionalized silica having mesopores by chemical tethering via hydrosillylative reaction in the presence of a Pt catalyst. The immobilized catalysts showed higher activity than their corresponding homogeneous catalyst towards the epoxidation of cyclooctene by tert-butylhydroperoxide, probably because of the improvement of the micro-environment around the titanium center. The reaction was found to be truly heterogeneous, since no further reaction proceeded after the separation of the catalyst by filtration. These catalysts also showed excellent catalytic activity for the epoxidation using hydrogen peroxide as an oxidant, while the parent homogeneous catalysts did not show any activity at all. (C) 2007 Elsevier Ltd. All rights reserved.