Layered double hydroxides (LDH) are generally regarded as ideal electrode materials for supercapacitors owing to high theoretical capacity. However, the inherently poor electronic conductivity and active site numbers limit their large scale applications. Herein, we synthesize MoO42− intercalated LDH heterostructure. The insertion of anions can increase the interlayer spacing, thereby increasing the interfacial active sites to adsorb many OH−. The optimized NiCoMoS@Mo0.75-LDH samples show a specific capacitance of 1158 C/g at 1 A/g. Furthermore, an assembled asymmetric supercapacitor presents an energy density at 2700 Wh/kg. Meanwhile, the device still shows a capacity loss of 9.87% after 10,000 cycles, revealing the potential applications in future energy storage devices.