The intermolecular hydrogen-bonding interaction and miscibility between enzymatically prepared novel polyphenols [poly(bisphenol A) and poly(p-tert-butyl phenol)] and poly(epsilon -caprolactone) (PCL) were investigated as a function of composition by Fourier transform infrared spectroscopy (FTIR) and DSC. The blend films of PCL and polyphenols were prepared by casting polymer solution. The FTIR spectra clearly indicated that PCL and polyphenols interact through strong intermolecular hydrogen bonds formed between the PCL carbonyls and the polyphenol hydroxyl groups. The melting point and degree of crystallinity of the PCL component decreased with an increased polyphenol content. A single glass-transition temperature was observed for the blend, and its value increased with the content of polyphenol, indicating that PCL and polyphenols are miscible in the amorphous state.