Living anionic polymerization has been a versatile technique for controlled synthesis of polymers with well-defined structures, e.g. block, graft, star, macromonomers and end-functionalized polymers. This technique allows one to control the molecular properties such as molecular weight, polydispersity, tacticity, and topology of the polymers, that ultimately helps in controlling the polymer properties. Anionic polymerization of methyl methacrylate is inherently complicated by side-reactions and proceeds in controlled manner only under carefully chosen conditions such as low temperature, polar solvent and bulky initiators. Moreover, the dynamics of ion-pair association equilibrium plays a major role in determining the degree of livingness of the system. This work involves synthesis and kinetic-study of living polymerization of MMA using anionic initiators in presence of Lewis acids as additives, synthesis of PMMA with hydroxyl end-functionality and utilization of these macroinitiators for the preparation of well-defined block copolymers, star-branched polymers and macromonomers.