An imidazolium-modified hexa-peri-hexabenzocoronene derivative (HBC-C11-MIM[Cl−]) was designed and synthesized as a stabilizer to fabricate reduced graphene oxide (RGO). The resulting RGO/HBC-C11-MIM[Cl−] hybrid shows excellent dispersivity (5.0 mg mL−1) and stability in water. RGO/HBC-C11-MIM[Cl−] was comprehensively characterized by using atomic force microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, thermogravimetric analysis, and Raman spectroscopy, thus revealing that one HBC-C11-MIM[Cl−] group can stabilize about 178 carbon atoms on the graphene sheets. The obtained hybrid film exhibits a high conductivity of 286 S m−1. Furthermore, the HBC-C11-MIM[Cl−]-modified RGO sheets can be readily dispersed in polar organic solvents upon exchange of the hydrophilic Cl− ions for hydrophobic bis(trifluoromethylsulfonyl) amide (NTf2−) ions.