Self-assembled monolayers (SAMs) of thiols with three different tail groups, -COOH, -SO3Na, and -NH2, were used to modify the Au substrates for electrodepositing polyaniline (PANI). Electrochemical quartz crystal microbalance (EQCM) results indicated a slower rate of deposition of PANI on a SAM surface consisting of positively charged amine groups compared to polymerization on bare gold and on a SAM of carboxyl acid groups. The properties of the SAM layers are dependent on the pH value of the solutions, and are effective only at very low pH values (pH < 2). A layer of the positively charged amino groups in acidic solution acted as a barrier for electron transfer in electro-oxidation of aniline monomer. The positively charged SAM of amine groups also increased repulsion between the coupled aniline species and the electrode surface and in this way hindered electrodeposition. Modification of the surface with pre-patterned SAMs have been demonstrated to be a convenient and practical way to fabricate selectively deposited thin films of polyaniline. (C) 2004 Elsevier Ltd. All rights reserved.