Supercapacitors, a promising kind of energy storage and transfer device for filling the gaps between traditional capacitors and lithium-ion batteries, are widely studied and used recently. A novel asymmetric supercapacitor was fabricated assembling Co3O4@RGO layer covered oxidized carbon fiber (OCF) and a mutil-layer OCF@Au@MnO2@PIn electrode. The multi-layer structure of these electrodes and the synergistic effects among each component were confirmed and guaranteed outstanding electrochemical performances. This novel supercapacitor shows excellent electrochemical performances with a high areal energy density of 1.83 mWh cm−2 at an areal power density of 3.2 mW cm−2 and long cycling life of 91.75% capacitance retention after 5000 cycles. Thus, this kind of portable supercapacitor with high performances not only might be used commercially but also provides a strategy for designing high-performance electrodes for supercapacitors.