The hydrogen bonding and miscibility behaviors of poly(2-vinylpyridine) (P2VP) or poly(4-vinylpyridine) (P4VP) with phenolic resin were investigated by differential scanning calorimetry and Fourier transform infrared spectroscopy (FTIR). These blends have a single glass transition over the entire composition range indicating that these blends are able to form a miscible phase due to the formation of intermolecular hydrogen bonding between hydroxyl of phenolic and pyridine ring of poly (vinylpyridines). Furthermore, FTIR studies on the hydrogen-bonding interaction between the hydroxyl group of phenolic and pyridine ring of poly (vinylpyridines) at various compositions and temperatures indicate that the greater inter-association for P4VP than P2VP due to the steric hindrance effect on specific interaction between these two polymers. Finally, inter-association equilibrium constants of phenolic/P2VP and phenolic/P4VP blends were determined by model compounds.