The blending behaviour of binary systems formed by the polymer component poly(N-vinyl-2-pyrrolidone) (PVP) and the low molecular weight compounds 4,4'-biphenol (44BP) and 2,2'-biphenol (22BP) was studied. The blends were characterized in the entire composition range by Differential Scanning Calorimetry (DSC), Fourier Transform Infrared Spectroscopy (FTIR), Thermogravimetric Analysis (TGA), and Scanning Electron Microscopy (SEM). Both, the glass transition temperature (Tg) and the melting point (Tm) of the pure components were affected as a consequence of the blending process. It was observed miscibility between the components in both blends and a higher interaction degree in the blend containing 44BP. FTIR analysis detected the hydrogen bonding as intermolecular interaction responsible of the observed miscibility, by means of the variation in the wave number corresponding to the stretching vibration of PVP carbonyl group. TGA and SEM analyses provided coherent and complementary results with both DSC and FTIR.