The interface widths in two immiscible polymer blend (Poly vinyl chloride (PVC)/Polystyrene (PS)) and PVC/Ethylene Vinyl Acetate (EVA) are determined experimentally using hydrodynamic interaction approach through free volume measurement by positron annihilation lifetime spectroscopy. For comparison, the same study is performed in a miscible blend (Styrene Acrylonitrile (SAN)/Poly Methyl Methacrylate (PMMA)). The interfacial width (?l) is evaluated from the hydrodynamic interaction (a) based on KirkwoodRisemann theory and friction coefficient from Stokes equation. Friction at the interface of a binary blend evidences how close the surfaces of the polymer chains come or stay apart which in turn depends on the type of force/interaction at the interface. In this work, we define interface width from a different perspective of FloryHuggins interaction approach. Measured composition dependent interface widths in the three blends studied clearly demonstrate the sensitivity of the present method. In miscible blend, high friction at the interface results in stronger hydrodynamic interaction and hence smaller interface widths (0.361.97 angstrom), whereas weak or no interaction in immiscible blends produce wider widths (2.8125.0 angstrom). (C) 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2012