Acrylamide and acrylic acid are grafted on graphene by free‐radical polymerization to produce a series of graphene–poly(acrylamide‐co‐acrylic acid) hybrid materials with different contents of graphene. The materials demonstrate shape memory effect and self‐healing ability when the content of graphene is in the range of 10%–30% even though poly(acrylamide‐co‐acrylic acid) itself had poor shape memory ability. The permanent shape of the materials can be recovered well after 20 cycles of cut and self‐healing. The result is attributed to the hard–soft design that can combine nonreversible “cross‐link” by grafting copolymer on graphene and reversible “cross‐link” utilizing the “zipper effect” of poly(acrylamide‐co‐acrylic acid) to form or dissociate the hydrogen‐bond network stimulated by external heating.
