A supramolecular hydrogel was prepared through the host–guest interaction between β-cyclodextrin (β-CD) and ferrocene (Fc) with two polymers as pendant groups. Reversible gel–sol transition was observed with the alternative stimuli of a positive potential (or an oxidant) and a negative potential (or a reductant). The hydrogel not only had good self-healing ability due to the dynamic host–guest interaction, but also was prepared under mild conditions and could respond to moderate electrochemical stimuli. Good biocompatibility endowed the hydrogel with potential practical and real-life applications, especially in tissue engineering and drug release field.