A binary transition metal oxides MnCo2O4 with hierarchical porous sphere structure (MnCo2O4 PSs) electrode material for supercapacitor was prepared by a moderate methanol solvothermal and calcination method. The MnCo2O4 PSs presents a large specific surface area (213.2 m2 g−1). Hierarchical porous sphere is beneficial for forming conductive networks and furnishing more electrochemically active sites. Amazingly, the MnCo2O4 PSs exhibits brilliant electrochemical properties that a relatively high specific capacitance of 1044 F g−1 and remarkable cycling stability (133.3% retention after 10000 cycles) are owned. A mimetic asymmetric supercapacitor (ASC) was constructed by the MnCo2O4 PSs and the starch-derived carbon foam material (SCF) as positive and negative electrode, respectively. The MnCo2O4 PSs//SCF ASC shows excellent specific energy (42.27 Wh kg−1) at the specific power of 400 W kg−1 under the optimal output potential difference of 1.6 V and long-term cycling stability. Herein, the MnCo2O4 PSs electrode material prepared in this work is a distinguished candidate material for supercapacitor.