The adsorbed process of ferrocene on a glassy carbon (GC) electrode modified by multi-walled carbon nanotubes (MWNTs) and electrochemical properties of the adsorbed layers are investigated. It is found that the redox process of ferrocene in solution is controlled by diffusion and surface electrochemical steps on the MWNT/GC electrode in contrast to the diffusion-controlled process of ferrocene on the GC electrode. The adsorbed ferrocene exhibits a pair of well-defined redox waves in the potential range from -0.2 V to 0.6 V Interestingly, two pairs of obvious redox waves for the adsorbed ferrocene are observed at the switching potential over 0.8 V and the peak current values of redox waves in more positive potential increase with the enlarging switching potential. The electrochemical reaction model of ferrocene adsorbed on the MWNT/GC electrode is proposed. (C) 2007 Elsevier B.V. All rights reserved.