Scanning tunnelling microscopy (STM), cyclic voltammetry (CV) and electron paramagnetic resonance spectroscopy (EPR) were used to investigate the influence of the TMP amine derivative on Au (1 1 1). The STM results show that the gold surface covered by the adlayer of the TMP derivative is easily modified (holes formation) after increasing the bias voltage to 0.5 V. The CV and EPR results show the electrochemical origin of observed STM topography changes. It is suggested that TMP could be oxidized to the nitroxyl TEMPO radical which adsorbs on Au in the form of an oxoammonium cation. Such an oxoammonium cation at the potential of 0.5 V forms a permanent complex of gold and the nitroxyl radical which could be easily desorbed during STM imaging. (C) 2008 Elsevier B. V. All rights reserved.