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Abstract Mechanically interlocked molecules are a class of compounds used for controlling directional movement when barriers can be raised and lowered using external stimuli. Applied voltages can turn on redox states to alter electrostatic barriers but their use for directing motion requires knowledge of their impact on the kinetics. Herein, we make the first measurements on the movement of cyclobis(paraquat‐p‐phenylene) (CBPQT⁴⁺) across the radical‐cation state of monopyrrolotetrathiafulvalene (MPTTF) in a [2]rotaxane using variable scan‐rate electrochemistry. The [2]rotaxane is designed in a way that directs CBPQT⁴⁺to a high‐energy co‐conformation upon oxidation of MPTTF to either the radical cation (MPTTF⋅⁺) or the dication (MPTTF²⁺).¹H NMR spectroscopic investigations carried out in acetonitrile at 298 K showed direct interconversion to the thermodynamically more stable ground‐state co‐conformation with CBPQT⁴⁺moving across the oxidized MPTTF²⁺electrostatic barrier. The electrochemical studies revealed that interconversion takes place by movement of CBPQT⁴⁺across both the MPTTF^•+(19.3 kcal mol⁻¹) and MPTTF²⁺(18.7 kcal mol⁻¹) barriers. The outcome of our studies shows that MPTTF has three accessible redox states that can be used to kinetically control the movement of the ring component in mechanically interlocked molecules.