Multilayers composed of zinc porphyrin, (Nafion (R))carbon nanotubes and viologen have been constructed on the substrate surfaces. The zinc porphyrin layer was covalently anchored on the surfaces via the pyridyl-CH2 bond, with the consecutive layers of negatively charged (Nafion (R)) carbon nanotubes and positively charged viologens assembled via the electrostatic interaction. The binding features for each layer were analyzed by using absorption and X-ray photoelectron spectroscopy, scanning electron microscopy as well as electrochemical analyzer. No significant difference was recorded for the porphyrin Soret band after the carbon nanotubes and viologens were assembled. The cyclic voltammograms showed a couple of redox waves centered at about -0.47 V vs Ag/AgCl, corresponding to bielectronic process of porphyrin. Another couple of redox wave was recorded when the layer of poly(p-xylyleneviologen) (PXV2n+) or methyl viologen (MV2+) was assembled, which was attributed to the one electronic process of PXV2n+ <-> PXVn(+o) or MV2+ <-> MV+o (c) 2007 Elsevier B.V. All rights reserved.