A six-station linear guest for cucurbit[7]uril and cucurbit[8]uril has been synthesized in order to implement a cascade of transformations driven by external stimuli. The guest chain is sequence-programmed with electron-deficient viologen and electron-rich naphthalene stations linked by either flexible or rigid spacers that affect the chain’s folding properties. Together with the orthogonal guest selectivity of the two cucurbiturils, these properties result in self-sorted cucurbituril pseudorotaxane foldamers. Each transformation is controlled by suitable chemical and redox inputs and leads not only to refolding of the guest chain, but also to the liberation of secondary messenger molecules which render the system presented here reminiscent of natural signaling cascades. The steps of the cascade are analyzed by UV/Vis, 1H NMR and electrospray (tandem) mass spectrometry to investigate the different pseudorotaxane structures in detail. With one guest oligomer, three different cucurbiturils, and several different chemical and redox inputs, a chemical system is created which exhibits complex behavior beyond the chemist’s paradigm of the pure chemical compound.