The synthesis of (a)lpha-ethyl beta-hexafluoroisopropyl itaconate (EFiPI) was performed. The polymerization of EFiPI initiated with dimethyl 2,2’-azobisisobutyrate (MAIB) was investigated kinetically in benzene. The polymerization rate (R(p)) was expressed by R(p) = k[MAIB](0.5)[EFiPI](2.0) at 50 degrees C. The overall activation energy of the polymerization was calculated to be a low value of 57.8 kJ/mol. Rate constants of propagation (k(p)) and termination (k(t)) were estimated under different polymerization conditions, using the ESR-determined concentrations of the propagating polymer radical. The increase in k(p) value (3.3-6.0 L/mol s) and the decrease in k(t) value (0.94-3.7 X 10(5) L/mol s) with monomer concentration are mainly responsible for the high dependence of R(p) on the monomer concentration. Activation energies of initiation (E(i)), propagation (E(p)), and termination (E(t)) were also determined : E(i) = 130.7 kJ/mol, E(p) = 18.0 kJ/mol, E(t) = 57.4 kJ/mol. The large apparent activation energy of termination is a main origin of low overall activation energy of the polymerization. Thermal behavior of the resulting poly(EFiPI) was investigated by differential scanning calorimetry (DSC) and dynamic thermogravimetry (TG). Copoly merization of EFiPI (M(1)) with St (M(2)) was also examined at 50 degrees C in benzene. The following copolymerization parameters were obtained according to the curve-fitting method : r(1) = 0.05, r(2) = 0.46, Q = 0.46, e = +1.14. Using these results, the rate constants of cross propagations in the copolymerization were estimated.