Methyl trans-beta-vinylacrylate (MVA) undergoes radical polymerization with alpha,alpha’-azo-bis(isobutyronitrile) (AIBN) in bulk and solution. The polymer obtained consists of 85% trans-1,4, and 15% trans-3,4 units. Poly(MVA) (PMVA) is readily soluble in common organic solvents, but insoluble in n-hexane and petroleum ether. PMVA exhibits a glass transition at 6 degrees C, and loses no weight up to 300 degrees C in nitrogen. The kinetics of MVA homopolymerization with AIBN was investigated in benzene. The rate of polymerization (R(p)) can be expressed by R(p) = k[AIBN](0.5)[MVA](1.0), and the overall activation energy has been calculated to be 94 kJ/mol. The propagation radical of MVA at 80 degrees C was detected by ESR spectroscopy, which indicated that the unpaired electron of the propagating radical was completely delocalized over the three allyl carbons. Furthermore, the steady-state concentration of the propagating radical of MVA at 60 degrees C was determined by ESR spectroscopy, and the propagation rate constant (k(p)) was calculated to be 1.25 X 10(2) L/mol . s. Monomer reactivity ratios in copolymerization of MVA (M(2)) with styrene (M(1)) are r(1) = 0.16 and r(2) = 4.9, from which Q and e values of MVA are calculated as 4.2 and -0.32, respectively.