The present invention provides cobaltosic oxide hierarchical structure nano array materials and a preparation method thereof, and an application of cobaltosic oxide hierarchical structure nano array materials. In a closed high temperature and high pressure reactor, redistilled water is taken as reaction solvent, cobalt salt, ammonium fluoride and urea are added into the reaction solvent for uniform mixing, and a reaction system is heated to generate a high-pressure environment to prepare cobaltous hydroxide precursor nanowire materials; then redistilled water is taken as reaction solvent, 2-methylimidazole is added into the reaction solvent, the cobaltous hydroxide precursor loaded on carbon cloth is immersed in the solution, the cobaltous hydroxide is taken as a cobalt source, the reaction system is heated and the reaction time is controlled to control a ZIF67 nucleation rate so as to prepare a cobalt-based metal organic framework (ZIF67) array; and finally, calcining decomposition ofthe cobalt-based metal organic framework (ZIF67) array is performed to obtain a cobaltosic oxide hierarchical structure. The product purity is high, the dispersibility is good, the controllability isgood, the production cost is low, the reproducibility is good, the cobaltosic oxide hierarchical structure nano array materials have cycling stability and large active surface area, and have a potential application value at the aspect of supercapacitors.