The blending of the functionalized vinyl polymer poly(4-vinylpyridine) (P4VPy) with the low molecular weight compounds 4,4'-biphenol (44BP) and 2,2'-biphenol (22BP) was studied. The binary systems formed by P4VPy and 44BP (blend A) and by P4VPy and 22BP (blend B) were characterized by Differential Scanning Calorimetry (DSC) to study the effect of the blending on characteristic transition, such as the glass transition of P4VPy and the melting of 44BP and 22BP. The results suggest the postulate that the components of both blends are miscible, with a comparatively higher intermolecular interaction level in the case of blend A. Using Fourier Transform Infrared Spectroscopy (FTIR), the formation of hydrogen bonding between the components of the blends A and B was detected. The behaviour observed with the FTIR corroborates the DSC results. Thermogravimetric Analysis (TGA) and Scanning Electron Microscopy (SEM) were used as additional analytical techniques and the results show a good agreement with the DSC and FTIR results and they complement the characterization of the studied systems.