It is recognized that an effective strategy to promote the industrialization of supercapacitors is to enhance the ion and electronic conductivities of electrode materials. In this work, it is demonstrated that the NO/NS-8 heterojunction material obtained via an epitaxial growth method based on ion exchange can be used as an outstanding electrode material for supercapacitors. The construction of heterojunctions between α-Ni(OH)2 and NiS1.97 allows the components to provide each other with ion or electron transport paths and endows NO/NS-8 with excellent ion and electron transport properties; this leads to a high utilization rate of active materials and an unprecedented high specific capacitance (up to 2375.8 F g-1 at 1 mV s-1 in a three-electrode system). Using the as-prepared NO/NS-8 heterojunction material as an electroactive material, an asymmetric supercapacitor with long cycle life (62.8% capacitance retention after 10 000 cycles at a current density of 5 A g-1) and high energy and power densities (128.4 W h kg-1 at a power density of 402.9 W kg-1 and 63.8 W h kg-1 at 7662.7 W kg-1) is finally demonstrated. This work provides a novel strategy for developing unique heterojunction materials for energy storage.