Cyclic voltammetry (CV) was employed to characterize the electrochemical behavior of polyelectrolyte brushes with immobilized electroactive counterions in response to external changes in concentration and composition of the supporting electrolyte and as a function of brush thickness. Poly(methacryloyloxy)ethyl-trimethyl-ammonium chloride (PMETAC) brushes were synthesized on An substrates via atom transfer radical polymerization followed by ion-exchange with ferricyanide, ions ([Fe(CN)(6)](3-)) as redox probes. CV measurements of the modified PMETAC brushes showed the typical electrochemical response corresponding to a surface-confined electroactive species and the redox counterions, as [Fe(CN)(6)](3-) species form stable ion pairs with the quaternary ammonium groups of the brush. The electron-transfer features of PMETAC brushes with different thicknesses, as characterized by CV and UV-vis spectroscopy, revealed that the charge density probed by CV was lower than the charge density measured by UV-vis spectroscopy. The electrode current decreased significantly with increasing concentration of supporting electrolyte due to the effect of the Donnan potential. Hydrophobic counterions, ClO4-, which induced brush collapse, lead to significantly reduced electrode currents.