Understanding and controlling electronic transfer in supramolecular structures is a major challenge for the realisation of new molecular electronic devices, such as organic field effect transistors. The supramolecular building blocks chosen for this study are pillar[5]arene rotaxanes, which have been immobilised as self-assembled monolayers (SAMs) on a gold surface.1 These systems incorporate ferrocene redox centres (Figure 1a), whose behaviour is probed by two complementary electrochemical methods : cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The very high kinetics of electron transfer in these systems requires working on ultramicroelectrodes and reaching high scan rates in CV as well as high frequencies in EIS. This CV/EIS crossover approach, together with an adapted representation of the impedance data, using capacitance diagrams (Figure 1b), highlights the complexity related to the organisation of the SAM and the electronic transfers. More specifically, it reveals the existence of thermodynamic and kinetic population distributions associated with variations in structure and interactions within these systems.1 These distributions are established by modelling equivalent electrical circuits in EIS, and reconstructing voltamograms in CV