Abstract The design of a dynamically assembled foldarotaxane was envisioned with the aim of operating as a two cascading trigger‐based molecular shuttle. Under acidic conditions, both the macrocycle and helix were localized around their respective best molecular stations because they are far enough from each other not to alter the stability of complexes. The pH‐dependent localization of the macrocycle along the encircled axle allowed us to modulate the association between the helical foldamer and its sites of interaction on the axle. Under kinetic control—at low concentration and room temperature—when the foldarotaxane supramolecular architecture is kinetically stable, the pH‐responsive translation of the macrocycle along the thread triggered the gliding of the helix away from its initial best station. At higher concentration—when helix assembly/disassembly process is accelerated—the system reached the equilibrium state. A new foldarotaxane isomer then appeared through the change of the relative position of the helix and macrocycle along the thread. In this isomer, the helix segregated the macrocycle away from its best station. The fine control of the kinetic and thermodynamic processes, combined with the control of pH, allowed the reciprocal segregation of the helix or the ring away from their respective best sites of interaction.< Leer menos