The miscibility of poly(vinyl chloride)/poly(methylmethacrylate) (PVC/PMMA) system was improved by introducing some pyrrolidone units into the main chains of PMMA. For that purpose, we have synthesized two copolymers of poly(methylmethacrylate-co-vinylpyrrolidone) (MMVP) through a radical polymerization and carried out a comparative study of PVC/MMVP blends by inverse gas chromatography (IGC) and differential scanning calorimetry (DSC) methods. The adequacy of seven n-alkane probes has been tested to determine the thermodynamic parameters. The miscibility of the two systems has been proved by a single Tg for each blend. This observation was also confirmed by DSC analysis. To highlight the presence of interaction and its intensity between PVC and MMVP in the blends, the polymerpolymer interaction parameters have been evaluated by IGC trough which the influence of the solute has been resolved. The Schneider approach confirmed the miscibility of these systems as the K deviates positively from unity. The miscibility has been appeared highlighted from the positive difference in surface energy between the pure polymers and their blends. (C) 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012