In present work, we demonstrate a rapid and easy approach to fabricate three-dimensional (3D) reduced graphene hydrogels (RGHs) by using thiourea dioxide as reducing agents in an aqueous solution of graphene oxide (GO) with ammonia. The transformation of GO suspension to the hydrogels can be confirmed by X-ray powder diffraction, Raman spectroscopy, and Fourier transform infrared spectroscopy. The hierarchical porosity, structure and surface chemical properties can be demonstrated by N2 sorption experiments, scanning electron microscopy and X-ray photoelectron spectroscopy. With adding different amounts of thiourea dioxide, the obtained RGHs behave different degree of reduction, controlled specific surface area and pore size distribution, and unlike performances in supercapacitors. Benefiting from well-defined and cross-linked 3D porous network architectures, the supercapacitors based on the RGHs in KOH electrolyte exhibited a high specific capacitance of 258.6, 167.3 and 198.3 F g−1 at 0.1 A g−1 for RGHs-1, RGHs-2 and RGHs-5, respectively. Furthermore, this capacitance also showed good electrochemical stability and a high degree of reversibility in the repetitive charge/discharge cycling test.