An investigation of the electrochemical behaviour of gold electrodes coated with poly(ethylene glycol) (PEG), poly(acrylic acid) (PAA) and nanopatterned PAA/PEG layers is presented. Plasma-enhanced chemical vapour deposition and colloidal lithography were used to produce nanodomes of PAA in a matrix of PEG. The electrochemical response at these nanostructured electrodes was studied as a function of the probe ion charge. Results show that the film structures allow the electrodes to retain their electrochemical activity while minimising surface fouling and will thus be useful in the development of electrochemical nanobiosensors for various applications. ; JRC.I.4-Nanotechnology and Molecular Imaging