Hydrogels with the properties of self-healing, toughness, stiffness and strength have great potential for use in smart materials. Herein, self-healing and tough hydrogels were successfully prepared after adding modified graphene oxide (GO) composites, which grafted the functional polymers onto the surface of GO. GO@polyacrylonitrile (GO@PAN) was synthesized via surface-initiated atom transfer radical polymerization (SI-ATRP) using GO@BiBB as the ATRP initiator. The nitrile group on GO@PAN was converted to pyridine, for which 2,4,6-triphenylpyrylium tetrafluoroborate (TPPT) was used as the photocatalyst. The prepared GO composite was added into polyacrylic acid (PAA) hydrogels formed by in situ radical polymerization. These tough hydrogels not only have high mechanical strength, but also show excellent self-healing performance. This strategy can provide a novel and universal route for the fabrication of smart hydrogels in biomedical and engineering fields.