By anchoring alkynylplatinum(II) terpyridine molecular tweezer/pyrene recognition motif on the chain-ends of telechelic polycaprolactone, high-molecular-weight supramolecular polymers have been successfully constructed via noncovalent chain extension, which demonstrate fascinating rheological and thermal properties. Moreover, the resulting assemblies exhibit interesting temperature- and solvent-responsive behaviors, which are promising for the development of adaptive functional materials.