A novel iron(III) porphyrin disulphide derivative have been successfully immobilised on gold surfaces by self-assembly. The redox response of the modified electrodes was compared with the obtained for a similar iron porphyrin in solution, confirming the immobilisation of the metalloporphyrin. The gravimetric data obtained by electrochemical quartz crystal microbalance (EQCM) during adsorption allowed an estimation of the electrode coverage, providing further evidence for the formation of the porphyrin SAM. The modified electrodes were also measured by conventional and imaging ellipsometry. The electrocatalytic activity of the two modified electrodes was tested for the reduction of the molecular oxygen. (C) 2002 Elsevier Science B.V. All rights reserved.