The interassociation constants of Painter-Coleman association model, obtained from the results of Fourier transform infrared spectroscopy of low molecular weight analogues in dilute solution, were used to predict the thermodynamic properties of phenolic and polyester polymer blends. The miscibility window, phase diagram, and degree of hydrogen bonding were discussed with the transferability of the association constant between the model compound and the polymer blends. All the predicted results coincided with the actual hydrogen bonding, regular photograph, and proton spin-lattice relaxation in the rotating flame (T1pH). This model provides a reasonable explanation of analogues of phenolic resin blends. The predicted thermodynamic properties are in harmony with the experimental results due to the high hydroxyl group density and low molecular weight of the phenolic resin which improves the compositional homogeneity of the phenolic/polyester blend.