In this work, the composite electrode composed of metal-organic frameworks and transition metal phosphides is first assembled on the nickel foam substrate. The as-prepared NiCo-MOF-74@Ni 12 P 5 /NF exhibits excellent performances with ultrahigh specific capacitance (12.8 F/cm 2 at 1 mA/cm 2 ), stable charge-discharge rate (82.8%), and excellent cycling stability (reserve 73.90% after 5000 charge and discharge cycles at 30 mA/cm 2 ), which are better than those of NiCo-MOF-74@NF without phosphating treatment of nickel foam. The corresponding hybrid supercapacitor (SC) device (NiCo-MOF-74@Ni 12 P 5 /NF//AC) delivers high storage capability (44.33 W·h/kg at 800 W/kg) and distinguished operating durability (83.04% after 5000 cycles). In addition, an all-solid-state hybrid SC successfully lit the LED for more than 2 min, which means that there is viable potential for practical applications in energy storage. The improved electrical properties are mainly due to the 3D heterostructure, the positive cooperative binding of nickel and cobalt elements, and the excellent electrical conductivity of the phosphide. As a result, this study proves the possibility of practical applications of NiCo-MOF-74@Ni 12 P 5 /NF electrodes for energy storage in hybrid SCs.