A water-soluble supramolecular polymer has been constructed from self-assembly of a heteroditopic monomer. It shows redox-responsiveness in the presence of a molecular chaperone. Furthermore, this supramolecular polymer material is shape-persistent and free-standing, which can be easily processed into various shapes. These unique features are all due to the dynamically reversible host–guest complexation and good mechanical properties of this supramolecular polymer, making it a platform to construct advanced and sophisticated materials. The formation of the supramolecular polymer was characterized by various techniques including two-dimensional diffusion-ordered NMR, scanning electron microscopy, and viscosity and rheology measurements.