Indium tin oxide (ITO) transparent electrodes were surface modified by a self-assembled monolayer of N-phenyl-gamma-aminopropyl-trimethoxysilane (PAPTS). Cyclic voltammetry of the PAPTS monolayer in aniline-free aqueous electrolyte showed the typical shape of a surface-confined monomer, due to the oxidation of the aniline moieties. This process resulted in a two-dimensional polyaniline film with uniform thickness of 1.3 nm, as measured by atomic force microscopy. X-ray photoelectron and UV-visible spectroscopic techniques confirm the formation of a conjugated polymer film. The influence of the surface modification of ITO electrodes on polyaniline electrochemical deposition was also studied. The initial oxidation rate of aniline increased in the PAPTS-modified ITO electrodes, although the overall film formation rate was lower than that of unmodified ITO electrodes. The morphology of the electrodeposited polyaniline films on PAPTS-modified and unmodified ITO electrodes was studied by atomic force microscopy. Films of smaller grain were grown in the PAPTS-modified ITO as compared to films grown on unmodified ITO. A blocking effect due to the propyl spacer is proposed to explain the reduced electron transfer in PAPTS-modified electrodes. (C) 2007 Elsevier B.V. All rights reserved.