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Chemoresponsive supramolecular systems with infinite switching capability are important for applications in recycled materials and intelligent devices. To attain this objective, here a chemoresponsive polypseudorotaxane is reported on the basis of a bis(p-phenylene)-34-crown-10 macrocycle (H) and a cyano-substituted viologen guest (G). H and G form a [2]pseudorotaxane (H⊃G) both in solution and in the solid state. Upon addition of AgSF6 , a polypseudorotaxane (denoted as [H⋅G⋅Ag]n ) forms as synergistically driven by host-guest complexa