A new route for liquefying graphene oxide (GO) into supramolecular ionic liquid (SIL) was proposed by the grafting of chloroacetic acid and the subsequent neutralization of carboxy groups with monofunctionalized polyetheramine (Jeffamine 2070). The rheological measurements verified its viscoelastic and liquid-like behavior. The peculiar phenomenon was mainly attributed to the formation of ionic bonds between the corona of chloroacetic acid and the canopy of Jeffamine. This type of highly viscous GO-based liquid possesses excellent amphiphilicity.