ATRP of a gelable monomer, 3-(triethoxysilyl)propyl methacrylate (TESPMA), mediated by CuBr/N,N,N’,N’’,N”-pentamethyldiethylenetriamine (PMDETA) using ethyl 2-bromoisobutyrate (2-EBiB) as initiator was studied. The results indicate that polymerization follows the first-order kinetic. PolyTESPMA (PTESPMA) is much more stable to moisture which is important for exploring the properties of its block copolymer. A series of PEO-b-PTESPMA block copolymers with different composition were prepared. Self-assembly of PEO-b-PTESPMA has also been explored in a mixture of methanol and water and polymeric vesicles have been obtained. By introducing the gelation catalyst, the block copolymer vesicles can be stabilized by the silica networks.