We report here the use of 4th and 5th generation dendrimers poly(propylene) imine (CU-D32 and CU-D64) as templating agents for the synthesis of mesoporous titanosilicate and vanadosilicate oxidation catalysts via sol-gel techniques. The physical properties of these mesoporous materials were characterized by TGA, BET, PXD and SEM/EDX analyses and these showed that the transition metals are evenly distributed throughout these silicates, which have interconnected spherical pores (approx. 12 Angstrom in diameter) and high surface areas of about 650 m(2) g(-1). Kinetic studies showed that all transition metal-doped catalysts were highly selective at oxidizing cyclohexene to the corresponding epoxide. Additionally, CU-D64-templated catalysts were more catalytically active for cyclohexene epoxidation than CU-D32-templated catalysts as a result of differences in pore size. All CU-D64-templated catalysts exhibited epoxidation catalytic activity comparable to that of titanium doped MCM-41 materials.