An asymmetric supercapacitor (ASC) uses very thin petal-shaped MnO2 nanosheets as the positive electrode and a network of carbon nanotube-embedded polyacrylonitrile-based carbon nanofibers (CNT-CNF electrodes) as the negative electrode. It has a high specific capacitance and a high specific energy density in 0.5 M Na2SO4. An assembled MnO2//CNT-CNF ASC is operated reversibly at a high cell voltage of 2.0 V and exhibits a high specific capacitance of 93.99 F g−1 and an excellent energy density of 52.22 Wh kg−1, which is better than those of ASCs that are based on MnO2//carbon, which can be found in the literature. The MnO2//CNT-CNF ASC has superior cycling stability with 92% retention of initial specific capacitance after 2000 cycles.