High-rate acetylene black (AB) decorated NiCo2S4 hollow microsphere is prepared via a gas bubble soft template and hydrothermal methodology. Benefiting from the combined advantages of the AB with high conductivity and the nanopetals assembled NiCo2S4 with unique hollow micro-/nano- structures, abundant porosity and high conductivity, the as-obtained composites are found to exhibit high specific capacitances (768Fg−1 at 2Ag−1) and remarkable rate capabilities (92.2, 80.1 and 70.3% of capacity retention rate at 20, 50 and 100Ag−1). The fabrication mechanism of the AB-NiCo2S4 composite is also proposed. Furthermore, an asymmetric supercapacitor is fabricated by using the AB-NiCo2S4 composite as a positive electrode and activated carbon as a negative electrode. Owing to the excellent electrochemical properties of the AB-NiCo2S4 electrode, the asymmetric device delivers high energy density (24.7Whkg−1) at a power density of 428Wkg−1 or high power density (17.12kWkg−1) at a reasonable energy density of 7.1Whkg−1, and exceptional cycling stability (105.6% of the initial capacity retention at 5Ag−1 over 5000 cycles). These results above demonstrate the significance and great potential of mesoporous NiCo2S4 hollow microsphere-based composites in the development of high-performance energy-storage systems.