The reactivity of electrogenerated benzyl radicals at carbon surfaces was examined through the cathodic reduction of the corresponding bromide derivatives. 4-Nitrobenzyl bromide and benzyl bromide were reduced in N,N-dimethylformamide (DMF) on highly ordered pyrolytic graphite (HOPG) surfaces. Electroproduced films were examined using electrochemistry, so :inning electron microscopy (SEM), and atomic force microscopy (AFM). Experiments show the formation of strongly adherent deposits and the occurrence of electrografting processes. They are based on radical generation and the reaction of the radical with the substrate. As expected, the thickness of the organic film increases with deposition time but the deposit displays a lower compactness than previously reported for the electroreduction of aryl diazonium salts. Interestingly for benzyl derivatives, the reduction potential required for the electrografting could be rendered much more positive by simply using an iodide-type supporting electrolyte.