Stereospecific living anionic polymerizations of methyl methacrylate are described with the focus on precise control of polymer structures such as molecular weight and its dispersity, tacticity and end-groups. In particular, recently developed efficient termination reaction with α- (chloromethyl) acrylates is discussed, which affords stereoregular poly (methyl methacrylate) s possessing α,β-unsaturated esters at the ω-ends. The subsequent thiol-ene click reaction resulted in a quantitative end-functionalization. The terminating reaction is also useful to evaluate reactivity of monomers and stereospecificity of propagating species in the presence of some additives.