This paper is devoted to the anionic polymerization of glycidyl methacrylate (GMA), using 1,1,4,4-tetraphenyl-1,4-dilithiobutane as the bifunctional initiator, at low temperature, in an aprotic solvent, and in the presence of the required amount of lithium chloride. This polymerization yields well defined polymers, exhibiting molar masses close to the expected ones, and narrow molar mass distributions. The oxirane ring remaining unaffected, the polymerization involves exclusively the methacrylic unsaturation of the monomer. Using this difunctional initiator, the synthesis of poly(GMA)-b-poly(MMA)-b-poly(GMA) triblock copolymers can be achieved. The central block of poly(MMA) (poly(methyl methacrylate)) is synthesized first, followed by the outer poly(GMA) blocks. All these materials have been characterized by analytical determination of the oxirane content, by size exclusion chromatography and by proton nuclear magnetic resonance, the latter method leading to the copolymer composition. The species formed are free of the corresponding homopolymers and their molar mass distributions are narrow and unimodal. Finally, new polymeric model networks have been synthesized by endlinking, upon addition of a small amount of ethylene dimethacrylate to the above bifunctional living precursor polymers.