This work presents original methodologies to estimate the electrochemical electron-transfer rate constants (k0) of immobilized electroactive species when strong intermolecular interactions occur in a redox-responsive material, for which the redox reaction is described by Butler–Volmer theory. Based on Laviron's equations and the initial Creager and Wooster’s work, these methodologies encompass the general lateral interaction model and have been experimentally tested to estimate k0 in order to provide evidence of the relevance and reliability of our approach.