The group transfer polymerization (GTP) with N-(trimethylsilyl)bis(trifluoromethanesulfonyl)imide (Me3SiNTf2) and 1-methoxy-1-triisopropylsiloxy-2-methyl-1-propene (iPr-SKA) has been studied using methyl acrylate (MA), ethyl acrylate (EA), n-butyl acrylate (nBA), 2-ethylhexyl acrylate (EHA), cyclohexyl acrylate (cHA), dicyclopentanyl acrylate (dcPA), tert-butyl acrylate (tBA), 2-methoxyethyl acrylate (MEA), 2-(2-ethoxyethoxy)ethyl acrylate (EEA), 2-(dimethylamino)ethyl acrylate (DMAEA), allyl acrylate (AlA), propargyl acrylate (PgA), 2-(triisopropylsiloxy)ethyl acrylate (TIPS-HEA), and triisopropylsilyl acrylate (TIPSA). Except for tBA and DMAEA, the GTPs of all other monomers described above proceeded rapidly in a living manner and produced well-defined homo acrylate polymers. The living nature of the GTPs of such acrylate monomers was further applied to the postpolymerizations of MA, EA, nBA, and MEA and also to the sequential GTPs of diverse acrylate monomers for preparing di- and multiblock acrylate polymers. In greater detail, the AB and BA diblock copolymers, (ABC)(4) dodecablock terpolymer, (ABCD)(3) dodecablock quaterpolymer, and ABCDEF hexablock sestopolymer were synthesized by sequential GTP methods using various acrylate monomers.