Abstract Heteroatom doping is an effective method to improve the capacitive performance of graphene-based materials. In this work, a facile and efficient radio-frequency (RF) plasma treatment strategy has been employed to achieve simultaneous doping and reduction of graphene oxide (GO). As a result, boron-doped and nitrogen-doped reduced graphene oxide (denoted as B-rGO and N-rGO) have been synthesized rapidly under relatively low temperatures compared with conventional thermal methods. The B-rGO and N-rGO present significantly improved specific capacitances as high as 345 F g⁻¹ and 365 F g⁻¹ at 0.2 A g⁻¹, respectively, exhibiting a fourfold increase compared to that of GO before plasma treatment. Interestingly, the N-rGO shows better rate capability than the B-rGO. Furthermore, the mechanism of simultaneous doping and reduction by RF plasma treatment is discussed based on the diagnosis of emission spectroscopy. The high energy electrons and plasma-excited ions and radicals render effective reduction, etching, and doping of GO at the same time. Compared with high-temperature carbonization and wet chemical methods, our plasma treatment method is more energy-saving and eco-friendly. We believe this rapid and straightforward plasma treatment method reported here can be extended to the incorporation of various heteroatoms into graphene lattice for broad applications.