In this study, reduced graphene oxide was functionalized with ethylenediamine (EDA) by a simple one-pot process, using a lithium ethylenediamine derivative as a nucleophilic reagent at 50 °C for 10 h. The presence of EDA chains in graphene was identified by Fourier transform infrared spectroscopy (FTIR), electronic energy loss spectroscopy (EELS), X-ray photoelectron spectroscopy (XPS), and zeta potential. By using the simple amidation reaction of EDA modified graphene and subsequent host–guest interactions between β-cyclodextrins (β-CDs) and polymers carrying guest moieties, we also synthesized a new type of graphene-based β-CD supramolecular hydrogels. The obtained hydrogels exhibited the gel-to-sol transition by adding a competitive guest sodium adamantine carboxylate (AdCNa) or competitive host α-CD.