In order to develop energy storage devices with high power and energy densities, electrodes should hold well-defined pathways for efficient Ionic and electronic transport. Herein, we demonstrate high-performance supercapacitors by building a three-dimensional (3D) macroporous structure that consists of chemically modified graphene (CMG). These 3D macroporous electrodes, namely, embossed-CMG (e-CMG) films, were fabricated by using polystyrene colloidal particles as a sacrificial template. Furthermore, for further capacitance boost, a thin layer of MnO2 was additionally deposited onto e-CMG. The porous graphene structure with a large surface area facilitates fast ionic transport within the electrode while preserving decent electronic conductivity and thus endows MnO2/e-CMG composite electrodes with excellent electrochemical properties such as a specific capacitance of 389 F/g at 1 A/g and 97.7% capacitance retention upon a current Increase to 35 A/g. Moreover, when the MnO2/e-CMG composite electrode was asymmetrically assembled with an e-CMG electrode, the assembled full cell shows remarkable cell performance: energy density of 44 Wh/kg, power density of 25 kW/kg, and excellent cycle life.