Supramolecular switches operate as simple machines by using a stimulus to turn stations off and on, generating thermodynamic differences that define bistability and enable motion. What has not been previously investigated, yet is required to gain further control over molecular movements for complex operations, is an understanding of how the same stimulus can also switch pathways off and on, thus, defining the kinetic property of bilability. To address this challenge, the mechanisms of the forward and return reactions of redox-switchable Cu(I)-based [2/3]pseudorotaxanes have been quantitatively characterized utilizing mechanistic cyclic voltammetry and employing a series of isosteric bis-bidentate ligands. First, the bistability of the switch is retained across the series of ligands: Reduction of the ligand drives the reaction forward where a [2]pseudorotaxane switches into a reduced [3]pseudorotaxane and reoxidation drives the switching cycle back to the beginning. Second, the switch is bilabile with the forward reaction following an association-activated interchange pathway (concerted), whereas the reverse reaction follows a different dissociation-based dethreading pathway (stepwise). The forward reaction is more sensitive to denticity (bidentate tetrazinyl ligand, k(2) = 12 000 M-1 s(-1), versus the monodentate pyrazinyl ligand, k(2) = 1500 M-1 s(-1)) than to electronics (k(2) = 12 000 M-1 s(-1) for methyl and trifluoromethyl substituents). The rate of return with the pyrazinyl ligand is k(1) = 50 s(-1). Consequently, both the mechanism and the thermodynamics of switching are stimuli dependent; they change with the oxidation state of the ligand. These findings have implications for the future design of molecular motors, which can be built from systems displaying allosterically coupled bistability and bilability.