Radical polymerization of captodatively substituted alkyl acylamidoacrylates was studied by pulsed laser polymerization using a N-2 laser. Propagation rate coefficient of the acrylates was varied with solvents used in spite of a radical mechanism, but little varied with methyl, n-propyl, and isopropyl substituents oil the acrylates. Arrhenius parameters for the propagation indicated that a solvent affected mostly on a frequency factor rather than a activation energy. In addition, it was suggested that these captodatively substituted propagating radicals were thermodynamically persistent but kinetically active in propagation, which resulted in rather smooth propagation in spite of bulky 1,1-disubstituted olefins. The mechanism of the polymerizations was discussed in detail on the basis of the kinetic studies and ESR spectroscopy. © 2005 Elsevier Ltd. All rights reserved.