Carbon-containing NiCo2S4 hollow-nanoflake structures were fabricated by a one-step solvothermal method using CS2 as a single source for sulfidation and carbonization. The reaction mechanism for the hollow structure with carbon residues was explored based on the formation of a bis(dithiocarbamate)-metal complex and the Kirkendall effect during solvothermal synthesis. The NiCo2S4 nanoflake electrode exhibited a high specific capacitance of 1722 F g-1 (specific capacity 688.8 C g-1) at a current density of 1 A g-1 and an excellent cycling stability (capacity retention of 98.8% after 10 000 cycles). The as-fabricated asymmetric supercapacitor based on NiCo2S4 nanoflakes and activated carbon electrodes revealed a high energy density of 38.3 W h kg-1 and a high power density of 8.0 kW kg-1 with a capacitance retention of 91.5% and a coulombic efficiency of 95.6% after 5000 cycles, highlighting its great potential for practical supercapacitor applications.