The effect of polymer structure on blend miscibility with polyvinylphenol (PVPh) has been studied for at least one polymer from a variety of polymer classes with potential hydrogen-bond accepting groups : polyesters (aliphatic and aromatic), polycarbonates, polyimides, polyamides, polysulfones, polyurethanes, polyethers, polysiloxanes, poly(amideimides), and cellulose esters. Many of the polyesters, polyamides, and cellulose esters showed evidence of interaction and miscibility with PVPh. In most of the other cases, there was no sign of miscibility. Generally good correlation exists between thermal behavior and infrared spectral data. Where there is significant interaction seen between the polymers by FTIR, substantial miscibility is seen by DSC analysis. In some cases, the phase behavior depended on the blend preparation scheme.