Aiming at an easy-processing metallo-supramolecular polymer which possesses the shape memory property and large deformation ability, we designed a simple metal coordination complex: the blends of zinc-neutralized carboxyl-terminated polybutadiene and poly(styrene-co-4-vinylpyridine) (PSVP). The two polymers are tightly bound due to the metal coordination interactions between Zn2+ ions from carboxyl-terminated poly butadiene and the pyridine group of the PSVP. The elastomer had reasonably good mechanical properties and was thermoplastic. Improvements in mechanical properties of the blends were realized in the rheology analysis compared with a blend without the introduction of the zinc salt. Small-angle X-ray scattering characterization showed that the microstructure of the elastomeric blend consisted of microphase-separated glassy nanodomains of principally PSVP, which served as cross-link junctions that were connected with polybutadiene chains. The elastomer exhibited good shape memory properties for large deformations, and its shape recovery efficiency could reach 81% in the first cycle and could reach 97% +/- 1% in the following seven cycles.