In this paper, nanostructured hierarchical mesoporous ribbon-like NiO was synthesized by a hard-template method combining the calcination process. Nickel sulfate hexahydrate, guanidine hydrochloride and mesoporous carbon were used as nickel precursors, precipitant of weak base and template, respectively. The resultant NiO samples were characterized by Raman spectroscopy, energy dispersive spectrometer, X-ray diffraction, N2 adsorption and desorption, scanning electron microscopy and transmission electron microscopy. The electrochemical performances were evaluated by cyclic voltammetry (CV), cyclic chronopotentiometry (CP) and electrochemical impedance spectroscopy (EIS) in 6M KOH solution. The typical hierarchical mesoporous ribbon-like NiO shows a good electrochemical performance: a high specific capacitance of 1260Fg−1 at 1Ag−1, 748Fg−1 at high current density of 20Ag−1 and 95% capacity retention at a current density of 10Ag−1 in a testing range of 5000 cycles.