Radical copolymerization of captodatively (cd) substituted methyl and ethyl 2-acetoxyacrylates (MAA and EAA) with electron-withdrawing olefins including vinylidene cyanide and acrylonitrile is studied using azobisisobutylonitrile as a radical initiator at 60 degreesC, and the structure of copolymers is examined by C-13 NMR spectra. It is found that the copolymerization of MAA and EAA with vinylidene cyanide provides a 1:1 alternating copolymer with epsilon -tacticity of 0.540 and 0.517, respectively, but that with acrylonitrile gives a random copolymer containing a larger amount of acetoxyacrylate unit. Addition of zinc chloride to the copolymerization of MAA and acrylonitrile, however, leads to the increase of acrylonitrile unit contents in the copolymer. Dielectric constant, gas permeability, and deformation by elongation of the copolymer film of MAA and vinylidene cyanide are also examined.