This paper describes the synthesis and the characterization of poly(phenylene oxide)-based nanoelectrode arrays. Using a hybrid organic/inorganic "sol-gel" solution, FTO (fluoro-tin-oxide) nanoelectrode arrays were synthesized with well-defined order, and controlled diameter of the nanoelectrode and the center-to-center distance. These FTO/ZrO2 nanoelectrodes were modified with ultrathin, polymer coatings based on the self-limiting electropolymerization of phenol. The polymer coated mainly the Fro nanoelectrodes. Impedance coupled with FTIR spectroscopies studies shows that the electrodeposited polymer coating is uniform, conformal and pin-hole free. The CP-AFM (conductive probe-AFM) imaging studies confirm that the ultrathin, uniform insulating poly(phenylene oxide) (PPO) layer homogeneously coats the FTO nanoelectrodes. (C) 2011 Elsevier Ltd. All rights reserved.