3D network-like mesoporous NiCo2O4 nanostructures have been successfully fabricated through a solvothermal route coupled with a post annealing treatment. Benefiting from its advantages of the unique 3D network-like structures with large specific surface area (170.6m2 g−1), abundant mesoporosity (5–10nm) and high electronic conductivity, the as-obtained NiCo2O4 manifests high specific capacitance of 931F g−1 at 3A g−1, remarkable capacity retention rate of 85.2 and 72.5% at 20 and 50A g−1 compared with 2A g−1 and superior cycling stability of 125.2% of initial capacity retention over 1000 cycles at 3A g−1. The excellent electrochemical performances coupled with its facile and cost-effective way will render the 3D network-like mesoporous NiCo2O4 nanostructures as attractive electrode materials for promising application in supercapacitors.