AbstractHomopolymerization behaviours of a series of α‐alkylacrylic methyl esters have been studied. With radical initiators α‐ethyl‐, α‐n‐propyl‐, α‐phenyl‐, and α‐benzylacrylate polymerize slowly to low polymers. These acrylates and α‐n‐butyl homolog underwent more rapid anionic polymerization to form high polymers in good yields at low temperatures. α‐i‐butylacrylate was also polymerized by anionic initiators to some extent. α‐i‐propyl, α‐sec‐butyl and α‐cyclohexylsubstitution inhibited both radical and anionic polymerizations of the esters. Some