The rational design of an efficient and stable electrocatalyst is the key to driving the oxygen evolution reaction (OER) in water electrolysis. Herein, we synthesized the CoFe/Ni/NM electrode in the amorphous/crystalline phase on a nickel mesh using an electrodeposition method. The prepared CoFe/Ni/NM electrode has a rich pore structure, and the overpotentials required to generate current densities of 10 mA cm−2 and 100 mA cm−2 were 235 mV and 361 mV in 1.0 M KOH, respectively, exhibiting excellent OER-catalytic activity with stability over 72 h. To simulate industrial production, we have tested the cell Ni/NM || CoFe/Ni/NM for overall electrolysis in 6.0 M KOH, which display a current density of 879 mA cm−2 at 90 °C and 2 V.