A simple alkyl lithium initiator (sBuLi) complexed with LiCl (10 molar equiv.) has been used to initiate the anionic polymerization of various methacrylic monomers, i.e. methyl methacrylate (MMA), tert-butyl methacrylate (tBuMA), glycidyl methacrylate (GMA), and dimethyl amino ethyl methacrylate (DMAEMA) in tetrahydrofuran at -78 degrees C. Only the homopolymerization of tBuMA proceeds in a living manner, as evidenced by both the linear plot of experimental molecular weight (M(nexp)) vs theoretical ones (M(ncal)) (slope congruent to 0.93) and monomer resumption experiments. However, three types of block copolymers, i.e. PtBuMA-b-PMMA, PtBuMA-b-PGMA, PtBuMA-b-PDMAEMA, have been successfully synthesized with a predictable molecular weight, and narrow molecular weight distribution.