A novel type of multi-stimuli responsive supramolecular polymer (MRSP) has been successfully constructed based on the self-assembly of heteroditopic macromonomers in a mixed solvent (CDCl3 : CD3CN = 2 : 1, v/v), which contain benzo-21-crown-7 (B21C7) host units and secondary ammonium salt guest moieties at each end of a poly(epsilon-caprolactone) (PCL) chain. Owing to the reversible host-guest complexation between B21C7 and the secondary ammonium salt, the resulting MRSPs exhibit multistimuli responsiveness to cations, pH, anions and temperature. More interestingly, nanofibers were facilely obtained via the solution electrospinning of a MRSP, which presented enhanced degradation behaviors in the presence of K+, Cl-, Et3N, or heating, indicating a multiple stimuli-responsive nature.