Nickel (Ni) always accumulates on multi-walled carbon nanotubes (MWCNT) by direct electrodeposition. In this paper, nickel nanoparticles were electrocrystallized on 4-nitroaniline (NA) radical monolayer-grafted on MWCNT through molecular level design. The structure and nature of the Ni/NA/MWCNT were characterized by field emission scanning electron microscope (FE-SEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), the results show that Ni nanoparticles were homogeneously electrodeposited on the surfaces of MWCNT. This complex catalyst showed excellent electro-catalytic activity for oxidation of ethanol in alkaline solution. (c) 2007 Elsevier B.V. All rights reserved.