The thermal degradation of the poly(ε-caprolactone) (PCL), poly(vinyl acetate) (PVAC), and their mixtures in solution has been investigated. The thermal degradation of PCL-PVAC mixtures with different PVAC concentrations (0, 35, 50, 70 wt %) was investigated at various temperatures (463-523 K) in an inert solvent (diphenyl ether). The molecular weight distributions of the polymers were determined using gel permeation chromatography (GPC). The experimental results indicated significant increase in the degradation rates of PVAC and a decrease in the degradation rates of PCL. This can be attributed to the proton-accepting nature of PCL and proton-donating nature of PVAC. A model based on continuous distribution kinetics was developed considering the interaction between the polymers through hydrogen abstraction. The degradation rate coefficients of the polymers and their mixtures were determined numerically by fitting the model to the experimental data.