Cyclic voltammetry (CV), Raman spectroscopy (RS), quartz crystal microbalance (QCMB) and electrochemical impedance spectroscopy (EIS) measurements were carried out in order to investigate the kinetics of the S-acetyl-calix[8]arene (S-Calix) adsorption, the structure of the layer formed on polycrystalline Au surface and its stability. The CV response recorded at Au/S-Calix modified electrode revealed an unusual time evolution of the surface coverage. The RS data corroborated with those provided by QCMB measurements proved the existence of multiple S-Au bonds in the structure of the S-Calix monolayer. The EIS was used to rationalize the kinetics of the monolayer formation and its reorganization. It was established that, due to the high affinity existing between the S and Au atoms and the remarkable flexibility of the calix[8]arene skeleton, the reorganization process consists in the increase of the number of S-Au bonds for the already adsorbed S-Calix molecules. (c) 2013 Elsevier Ltd. All rights reserved.