The kinetics of polymerization of ε-caprolactone (CL) in bulk was studied by irradiating with microwave of 350 W and frequency of 2.45 GHz with different cycle-heating periods (30-50 s). The molecular weight distributions were determined as a function of reaction time by gel permeation chromatography. Because the temperature of the system continuously varied with reaction time, a model based on continuous distribution kinetics with time/temperature-dependent rate coefficients was proposed. To quantify the effect of microwave on polymerization, experiments were conducted under thermal heating. The polymerization was also investigated with thermal and microwave heating in the presence of zinc catalyst. The activation energies determined from temperature-dependent rate coefficients for pure thermal heating, thermally aided catalytic polymerization, and microwave-aided catalytic polymerization were 24.3, 13.4, and 5.7 kcal/mol, respectively. This indicates that microwaves increase the polymerization rate by lowering the activation energy.