Propagation kinetics of vinyl acetate (VAc) free-radical homopolymerization in bulk and in solution of 40 wt % CO2 have been studied by the PLP-SEC method at pressures up to 1500 bar. The molecular weight distributions of the polymer samples show well-resolved pulsed-laser induced structure with at least two, in most cases even three distinct inflection points. At the p and T conditions of this work, no difference is seen in propagation rate coefficients, kp, of VAc in solution of carbon dioxide and in bulk. The activation volume for kp at 25°C in both reaction media is DV # = - (10.2 ± 0.9) cm3×mol–1.