New metallosilicate catalysts were prepared by reacting a silanol capped dendrimer. Si[CH2CH2Si(CH3)(2)OH](4) with MCp2Cl2 (M = Ti-IV, Mo-VI, W-VI and V-V). The resulting Si[CH2CH2Si(CH3)(2)OMCp2Cl](4) compounds were incorporated in a silica matrix by the sol-gel method. The catalytic activity of the metallosilicates after calcination revealed excellent activity and selectivity towards epoxidation of alkenes with tert-butylhydroperoxide. Maximum activity was observed with molybdenum-containing materials. Analysis of the catalytic activity revealed that the catalysts were truly heterogeneous.