For high performance supercapacitors, novel hierarchical yolk-shell -Ni(OH) /Mn O microspheres were controllably synthesized using a facile two-step method based on the solvothermal treatment. The unique -Ni(OH) based yolk-shell microstructures decorated with numerous interconnected nanosheets and the hetero-composition features can synergistically enhance reactive site exposure and electron conduction within the microspheres, facilitate charge transfer between electrolyte and electrode materials, and release structural stress during OH chemisorption/desorption. Moreover, the Mn O sediments distributed over the -Ni(OH) microspheres can serve as an effective protective layer for electrochemical reactions. Consequently, when tested in 1 mol·L KOH aqueous electrolyte for supercapacitors, the yolk-shell -Ni(OH) /Mn O microspheres exhibited a considerably high specific capacitance of 2228.6 F·g at 1 A·g and an impressive capacitance retention of 77.7% after 3000 cycles at 10 A·g . The proposed -Ni(OH) /Mn O microspheres with hetero-composition and unique hierarchical yolk-shell microstructures are highly promising to be used as electrode materials in supercapacitors and other energy storage devices.