In this work, pristine multiwalled carbon nanotubes (MWNTs) were functionalized by utilizing the free radicals generated through Bergman cyclization of enediyne containing compounds 3. Polyesters were subsequently grafted from the surface of MWNTs through ring-opening polymerization of epsilon-caprolactone or lactide initiated by free hydroxy groups generated after hydrolysis of ester groups. Functionalized MWNTs were characterized with a variety of techniques, including TGA, NMR, IR, UV-vis, TEM, and Raman spectroscopy. After surface modification, MWNTs showed good solubility in common organic solvents and polymer solutions. Fabrication of MWNTs polymer nanocomposites was revealed through electrospinning with polycaprolactone. (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 5541-5548, 2010