Interfacial properties of single-walled carbon nanotubes (SWCNTs) were modified by covalent surface modification of the nanotubes with an ATRP initiator which is able to polymerize acrylic monomers. This methodology starts with the incorporation of 2-phenyl-1-ethanol through a diazotization reaction. Further modification drives to an ATRP initiator, (4-(2-bromo-2-methylpropanoate of 1-hydroxyethyl) phenylidene) which is covalently linked to the surface of the SWCNT. This ?-haloester linked to the surface of the SWCNT can be analysed, quantified and used as an initiator in the ATRP polymerization methodology without the addition of the sacrificial initiator. Well control of the molecular weights of the acrylic polymers grown on the surface of SWCNT was obtained. Furthermore, the polymer characterization by FT-IR, NMR CP-MAS, thermo gravimetric analysis and Transmission Microscopy as well as all the intermediates are reported. © 2013 Taylor & Francis.