AbstractMechanically tough and self-healable polymeric materials have found widespread applications in a sustainable future. However, coherent strategies for mechanically tough self-healing polymers are still lacking due to a trade-off relationship between mechanical robustness and viscoelasticity. Here, we disclose a toughening strategy for self-healing elastomers crosslinked by metal–ligand coordination. Emphasis was placed on the effects of counter anions on the dynamic mechanical behaviors of polymer networks. As the coordinating ability of the counter anion increases, the binding of the anion leads to slower dynamics, thus limiting the stretchability and increasing the stiffness. Additionally, multimodal anions that can have diverse coordination modes provide unexpected dynamicity. By simply mixing multimodal and non-coordinating anions, we found a significant synergistic effect on mechanical toughness ( > 3 fold) and self-healing efficiency, which provides new insights into the design of coordination-based tough self-healing polymers.