Transition metal layered double hydroxides (LDHs) with amazing theoretical capacitance have caused remarkable interest as a potential supercapacitor electrode materials. However, the exerted low performance limits their further application. Nano-engineering technology was considered to be an effective strategy to further expose the pseudocapacitive properties of materials. Here, an ordered NiV [email protected] nanoarray was successfully constructed via phosphorized pretreatment and hydrothermal growth method. The as prepared NiV [email protected] electrode delivers an areal capacitance of 2.85 F cm−2 at the current density of 20 mA cm−2 and rarely decrease capacitance after over 5000 cycles at 50 mA cm−2. Furthermore, the asymmetric supercapacitor assembled with prepared NiV [email protected] as the positive electrode and activated carbon as the negative electrode was found to show a maximum energy density of 0.202 mWh cm−2 under a power density of 7.022 mW cm−2. This work suggests that the NiV [email protected] nano-arrays electrode can be regard as the remarkable candidate to improve the performance of the asymmetric supercapacitor.