Mesoporous Ti-, Cr- and V-substituted derivatives of the cubic silica molecular sieve MCM-48 have been hydrothermally synthesized at 373 K by an electrostatic assembly pathway using cetyltrimethylammonium cation as the templating agent. The transition metal substituted products all exhibit improved crystallinity and a narrower pore size distribution relative to the pristine molecular sieve. Transition metal substitution caused an enlargement of the cubic unit cell as well as an increase in the degree of crosslinking in the mesopore walls. The coordination of V-sites in the meso-structure is exclusively tetrahedral, as judged by NMR spectroscopy. These sites as well as those of Ti and Cr sites are active and selective for the peroxide oxidation of styrene and methyl methacrylate to benzaldehyde and methyl pyruvate, respectively.