In the present investigation, we have studied polymerization of (a) vinylpyrrolidone (VP) and (b) VP with C60 molecule applying various supercritical conditions with 2,2-azobisisobutyronitrile (AIBN) as a catalyst. Products hence obtained are polyvinylpyrrolidone (PVP) and fullerene-polyvinylpyrrolidone (C60/PVP) polymers. With polymerization reaction, the yield of corresponding C60-PVP polymers was significantly affected under applied concentrations of AIBN (304.5-1218.0 x 10(-3) mol/dL) supercritical pressure (1200-1800 psi), temperature (C60 90 +/- 1 degrees) and time (3-6 h). The concentration of VP ranged 7.04-12.59 x 10(-3) mol/dL. The samples of the synthesized C60/PVP polymer with lowest (24.8%) and highest (45.0%) yields were characterized using UV-Vis, FT-IR, H-1 NMR, laser-induced breakdown spectra, scanning electron microscopy and simultaneous TG-DTA-DSC. The morphology of the C60/PVP polymers was confirmed by scanning electron micrographs which indicates the existence of separated C60 phases with heterogeneous morphology in corresponding C60/PVP polymers in all the cases. Simultaneous TG-DTA-DSC revealed enhanced thermal stability of C60/PVP.