Fluorine-containing groups represent very promising functionalities because fluorine not only changes the physico-chemical properties of the graphene surface, it may also alter its electronic and magnetic properties. Herein, we describe, for the first time, the synthesis and characterization of the perfluoroalkyl functionalization of graphene oxide by a simple and general solution-based process using perfluorooctyl functionalized aniline (R_F-NH₂) as both reducing and grafting reagent. Importantly, the perfluoroalkyl functionalized graphene hydrogels (FGHs) could be achieved by a hydrothermal method. The as-fabricated FGHs exhibited outstanding absorption ability and electrochemical performances, including ultrahigh specific capacitances of 321.6 F g⁻¹ and excellent cycling stability in aqueous and organic electrolytes. The changes in the electronic structure of the perfluoroalkyl functionalized graphene were also simulated by density functional theory.