A two-dimensional conducting polyaniline (PAN) monolayer has been formed on an electrically insulating monolayer. The approach is based on the electrochemical polymerization of surface-confined anilinium ions that were electrostatically attached to a negatively charged self-assembled monolayer of omega-mercaptodecanesulfonate (MDS), HS(CH2)(10)SO3-, on a gold surface. The formation and characterization of the two-dimensional film and the MDS monolayer have been examined by cyclic voltammetry, Fourier transform IR spectroscopy, X-ray photoelectron spectroscopy, wettability, and scanning electrochemical microscope. The formation of a capacitor-like assembly, in which electron transfer was blocked between PAN and the gold surface, was accomplished by electrochemically incorporating hexadecanethiol (C-16) into the MDS monolayer. The PAN monolayer exhibits properties similar to those of a thin polymer film.