Confronted with the pressing issue of energy scarcity, the development of an economical and potent bifunctional catalyst is of paramount importance. We adopt an interface engineering strategy to modify the surface of NiFe‐LDH nanoplates with O2 plasma treatment. This process enhances the local electric field of NiFe‐LDH, resulting in the formation of a self‐assembled polycrystalline nanowire array on the nanoplate surface. After O2 plasma treatment for 30 min, the NiFe‐LDH‐P30 not only formed a heterostructure with rough surface, but also regulated the exposure of crystal surfaces. Due to the strong interface coupling between the self‐assembled 3D nanoflowers, 2D nanoplates and 1D nanowires, the NiFe‐LDH‐P30 exhibits an excellent structural stability. Moreover, it demonstrated exceptional HER and OER activities in alkaline condition, achieving a low overpotentials of 154 mV and 242 mV at 10 mA cm‐2, respectively. Furthermore, NiFe‐LDH‐P30 as the dual‐electrode material for the cathode and anode in the process of water splitting results in a low voltage of 1.63 V at a current density of 10 mA cm‐2. Through the strategic application of interface engineering, this work has pioneered a novel approach to the creation of transition metal‐based electrocatalysts, which is benefit to a range of practical energy applications.