This article overviews the polymer chemistry of acrylates designed for functional-group synergy among the vinyl group and ester- and alpha-substituents. alpha-Substituents have been incorporated to tune the reactivity of the vinyl group; for example, ethyl alpha-cyanoacrylate, known as instant adhesions, has high reactivity to initiate anionic polymerization using moisture. Moreover, alpha-acyloxyacrylates undergo radical polymerization, increasing the degree of polymerization in proportion to monomer conversions due to the stabilized radical species by the captodative effect. alpha-Arylacrylates produced alternating copolymers with methyl methacrylate (MMA) using anionic polymerization, which exhibited specific fluorescence. alpha-(Aminomethyl)acrylates stabilized by intramolecular hydrogen bonding yielded a pH-/thermo-responsive polymer. Anionic polymerization of alpha-(alkoxymethyl)acrylates resulted in high isotacticity due to the chelating effect at the propagating chain end. alpha-(Halomethyl)acrylates underwent a nucleophilic conjugate substation reaction, applied to end-functionalization, polycondensation, and polymer degradation. For a long time, ring-opening polymerization of cyclic acrylates has been considered difficult; however, it was recently achieved using sophisticated monomer design.