Featured Application: The prepared three-dimensional graphene with porous structure and high electrical conductivity is an ideal electrode material for electrochemical energy storage devices, including supercapacitors and lithium ion batteries, etc.Abstract: Preparation of pure three-dimensional graphene (3DG) with high rate performance for supercapacitors is critical for fast rate charge/discharge. Here, 3DG was prepared via thermal annealing of freeze-dried reduced graphene oxide (RGO) hydrogel under inert gas protection. The formed 3DG as an electrode material for supercapacitors revealed a specific capacitance of 115 F·g −1 at a current density of 1 A·g −1 , and a high capacitance retention of 70% as current density increased to 40 A·g −1 . The excellent rate capability was mainly attributed to the reserved porous structure and higher electrical conductivity for 3DG after thermal reduction than its RGO hydrogel precursor.