Multilayered graphene/MnO2 nanocomposite electrode prepared by anodic electrodeposition and electrophoresis exhibited superior capacitive behavior compared to the bare MnO2 and graphene electrodes. The multilayered architecture provided both the horizontal and vertical channels for electrolyte access during fast charging and discharging. The graphene layer turned out to play an important role in enhancing the electron conduction in the multilayered architecture. Therefore, the improved electrochemical behavior might result from the significantly improved ion transport and electron conduction in the multilayered architecture of the graphene/MnO2 composite electrode. Furthermore, the MnO2 nanowire layer coated on the graphene layer could significantly suppress the oxygen evolution reaction, broadening the potential window of water stability.