Cone-shaped CuS@MnS nanostructures were grown on Ni foam with robust adhesion using a one-step hydrothermal method and efficiently served as binder-free battery-type material for high-performance supercapacitors. The synergic effects of the unique nanostructure and great adhesion is advantageous for enhancing the surface area on the Ni foam substrate, increasing the storage and charge accumulation, increasing the electrochemical activity between CuS and MnS, and accelerating electron and electrolyte ion transfer. As a result, as a battery-type material, the CuS@MnS/NF composite electrode exhibited excellent electrochemical performance, including high specific capacity (89.77 mA h g−1 at a current density of 1 A g−1), good cycling stability (95.9% capacity retention after 3000 cycles), and outstanding rate capability compared to that of CuS/NF (45.73 mA h g−1) and MnS/NF (3.8 mA h g−1). This study sheds new light on the composites, and demonstrates that the CuS@MnS/NF electrode is an ideal material for electrochemical energy storage.