Vapor-grown carbon nanofibers (CNFs) were oxidized and functionalized for atom transfer radical polymerization (ATRP) of tert-butyl acrylate (t-BA) from the surface of the CNFs. The materials were characterized by solubility tests, Fourier-transform infrared (FTIR) spectroscopy, Raman spectroscopy, thermogravimetric analysis (TGA), X-ray diffraction (XRD), and scanning electron microscopy. The FTIR and electron microscopy results suggest that ATRP process was successfully used to graft poly(tert-butyl acrylate) (poly(t-BA)) chains from the surface of the fibers. Raman results strongly indicate the partial degradation of the graphitic layer of CNFs because of the chemical treatments. TGA results suggest that the presence of poly(t-BA) leads to a decrease of the initial degradation temperature of the fibers. XRD and electron microscopy results indicate that the microstructure of fibers was not destroyed because of the oxidation and functionalization processes. (C) 2008 Wiley Periodicals, Inc.