Mesoporous [email protected]2O4 composite materials have been fabricated via a facile strategy including solvothermal synthesis of Ni-P and subsequent chemical deposition of NiCo2O4. Due to the synergistic effect between Ni-P and NiCo2O4, the [email protected]2O4 composite materials exhibit an enhanced performance (1240 F g−1 at 1 A g−1, 668 F g−1 at 16 A g−1) compared with the bare Ni-P materials (717 F g−1 at 1 A g−1, 106 F g−1 at 16 A g−1) and NiCo2O4 materials (741 F g−1 at 1 A g−1, 457 F g−1 at 16 A g−1). Furthermore, the AC//[email protected]2O4 asymmetric capacitor exhibits superior energy/power densities (13.3 Wh kg−1/5.7 kW kg−1) and cycling behavior (78.3% retention after 10,000 cycles at 4 A g−1) than the AC//Ni-P asymmetric capacitor (7.4 Wh kg−1/5.7 kW kg−1, 63.4% retention after 10,000 cycles at 4 A g−1) and AC//NiCo2O4 asymmetric capacitor (10.4 Wh kg−1/5.6 kW kg−1, 32.4% retention after 10,000 cycles at 4 A g−1). The high performance makes the mesoporous [email protected]2O4 composite materials promising electrode materials for supercapacitors.