The impact of the structure of electrode surface on the behaviour of tetrabutylammonium cations on gold (100) and (111) electrodes has been studied using the cyclic voltammetry and differential capacity measurements. The adsorption features of these cations were found to be structure sensitive and resemble those of simple organic molecules rather than those of ions. It was also suggested that adsorption of anions from supporting electrolyte lifts the reconstruction which is modified by the tetrabutylammonium cations on the surface. (C) 2014 Elsevier B.V. All rights reserved.