Oxygen evolution reaction (OER) is considered as the bottleneck of electrochemical water splitting because of its sluggish kinetics. Therefore, the design and synthesis of highly active, low-cost, and stable electrocatalysts for the OER is the greatest challenge in electrochemical water splitting. Here, an amorphous heterogeneous NiFe-LDH@Co(OH) 2 @NF with abundant active sites is fabricated by a step-wise electrodeposition technique. Firstly, Co(OH) 2 is directly deposited onto nickel foam (NF) substrate by a electrodeposition technique. Secondly, NiFe-layered double hydroxide (NiFe-LDH) is further covered on the surface of Co(OH) 2 to obtain the heterogeneous NiFe-LDH@Co(OH) 2 @NF electrocatalyst. The thickness of NiFe-LDH can be controlled by changing the time of electrochemical deposition. Benefiting from the amorphous structure and the positive synergies between NiFe-LDH and Co(OH) 2 , the optimized NiFe-LDH@Co(OH) 2 @NF-300 shows high electrocatalysis activity. In the 1 M KOH solution, the overpotential for OER is only 130 mV (at 10 mA cm −2 ). Remarkably, serving as a bifunctional electrode in alkaline electrolyzer, it only needs 1.6 V to reach the current density of 10 mA cm −2 . The work provides a simple and viable technical solution for fabricating non-noble electrocatalysts with excellent performance for electrochemical water splitting.