We present an alternative routine by constructing a novel architecture, conductive metal/transition oxide (Co@Co3 O4 ) core-shell three-dimensional nano-network (3DN) by surface oxidating Co 3DN in situ, for high-performance electrochemical capacitors. It is found that the Co@Co3 O4 core-shell 3DN consists of petal-like nanosheets with thickness of <10 nm interconnected forming a 3D porous nanostructure, which preserves the original morphology of Co 3DN well. X-ray photoelectron spectroscopy by polishing the specimen layer by layer reveals that the Co@Co3 O4 nano-network is core-shell-like structure. In the application of electrochemical capacitors, the electrodes exhibit a high specific capacitance of 1049 F g(-1) at scan rate of 2 mV/s with capacitance retention of ∼52.05% (546 F g(-1) at scan rate of 100 mV) and relative high areal mass density of 850 F g(-1) at areal mass of 3.52 mg/cm(2) . It is believed that the good electrochemical behaviors mainly originate from its extremely high specific surface area and underneath core-Co "conductive network". The high specific surface area enables more electroactive sites for efficient Faradaic redox reactions and thus enhances ion and electron diffusion. The underneath core-Co "conductive network" enables an ultrafast electron transport.