The development of functional materials and smart surfaces has received tremendous attention in recent years. The anchoring of molecular machines and the transfer of their properties on to solid substrates may facilitate the design of new smart devices. Herein, we report an approach to the covalent modification of glassy carbon electrodes with electrochemically responsive tris(N-phenylureido)calix[6] arene-based pseudorotaxanes. The main focus of this study has been the electrochemically driven threading/de-threading process of the redox active dialkylviologen axial comporient of the supramolecular assemble. After the creation of an amine monolayer on the electrode, pseudorotaxane systems were generated at the surface using different approaches. It was revealed, through electrochemical investigations, that the reversibility of the threading/de-threading process of the axle depended on the nature of the alkyl substituents on the axle. (C) 2016 Elsevier Ltd. All rights reserved.