A series of graphene materials are prepared by intercalation of graphene oxide (GO) with different surfactants, cetyltrimethylammonium bromide (CTAB), n-octyltrimethylammonium bromide, tetramethylammonium bromide, and sodium dodecylbenzene sulfonate, subsequently by gamma-ray induced reduction in N-methyl-2-pyrrolidone (NMP) at room temperature. GO can be reduced by the electrons generated from the radiolysis of NMP under gamma-ray irradiation, and reduced GO is simultaneously functionalized by the radiolytic product of NMP. Cationic surfactant CTAB with longer alkyl chains can effectively promote the reduction process of GO by preventing the aggregation of graphene sheets, which has been testified by X-ray photoelectron spectroscopy, X-ray diffraction, thermogravimetric analysis, Raman spectroscopy, and Fourier transform infrared spectroscopy analyses. Furthermore, when the as-prepared graphene/polyaniline composites are used for supercapacitor electrode materials, there is a highest specific capacitance of 484 F g(-1) at a current density of 0.1 A g(-1) for the graphene produced in the presence of cationic surfactant CTAB.