Multilayers film of nanostructured gold nanoparticles (AuNPs) has been fabricated based on the layer-by-layer (LBL) technique using a self-assembled monolayer of 5,15-di-[p-(6-mercaptohexyl)-phenyl]-10,20-diphenylporphyrin (trans-PPS2). AuNPs act as physical cross-link points in the multilayers. Electrochemical impedance spectroscopy (EIS) and scanning electrochemical microscopy (SECM) are applied to study the formation of the organic-inorganic multilayers film and have determined the electrochemical parameters, i.e., the heterogeneous electron transfer rate constant (K-et). The observed phenomena indicate that the electron transfer (ET) process is affected by material properties and the molecular structure of self-assembled monolayers (SAMs). Using the high sensitivity of ET of ferricyanide to the modification of the gold surface with multilayers film, we select this reaction as a probe to study the different modification stages at this modified electrode. ET is retarded on the trans-PPS2 alternative deposition of layers on the electrode surface and is accelerated on the AuNPs' layers. SECM images are used to collect surface information in the course of the successive modification process. SECM images obtained from bare and different modification stages show very high resolution with different topographies. (C) 2010 Published by Elsevier Ltd.