In this paper, freestanding one-dimensional MnO2 nanoflakes are successful prepared through a simple hydrothermal reaction by using the carbon shell of TiC/C core/shell arrays as the sacrificial template. Its structure and morphology are characterized by X-ray diffractometer, X-ray photoelectron spectroscopy, Raman spectroscopy, scanning electron microscopy, energy dispersive X-ray spectrometer and transmission electron microscopy. Results show that the thickness of the carbon shell decreased but also remained and the ultrathin MnO2 nanoflakes with thickness less than 5 nm uniformly grow on the surfaces of the TiC/C nanowire to form a core/double shell structure after the hydrothermal reaction. The electrochemical performance of the as-prepared electrode is evaluated by cyclic voltammetrys, galvanostatic charging-discharging tests and electrochemical impedance spectroscopy, and high capacities, excellent rate capabilities and exemplary cycling performance is obtained. The as-prepared electrode shows a high specific capacitance of 598.8 F g−1 and 85.8% of its initial capacitance is retained after 10,000 cycles at a high discharge current density of 10 A g−1, suggesting that this structure has a promising future as high-performance supercapacitor electrode.