The electrochemical properties of ferrocene (Fc) on a glassy carbon (GC) electrode modified by multi-walled carbon nanotubes (MWNTs) in the presence and absence of surfactants have been investigated by progressively voltammetric sweeping. Dihexadecyl phosphate (DHP) and hexadecyl trismethyl ammonium chloride (HTAC) are found to impact the redox reactions of Fc adsorbed on MWNT surfaces. An excess amount of DHP dispatches Fc from MWNTs surfaces, leading to weakly adsorbed configuration of Fc. The formal potential of the adsorbed Fc in the presence of DHP shifts to a lower potential. Cationic surfactant HTAC on MWNT surfaces depresses the redox reactions corresponding to the weakly adsorbed configuration of Fe. It becomes evident that the configuration and hence redox reactions of Fc depend strongly on the presence and concentrations of surfactants on the electrode surfaces and in the buffer solutions. (C) 2009 Elsevier BM. All rights reserved.