Active and stable electrocatalysts are the key to water electrolysis for hydrogen production. This paper reports a facile direct growth method to synthesize NiFe-layered double hydroxides (LDHs) on nickel foil as an electrocatalyst for the oxygen evolution reaction. The NiFe-LDH is synthesized by a galvanic process at room temperature without any additional energy for synthesis. The synthesized NiFe-LDH is a karst landform with abundant active sites and efficient mass diffusion. The NiFe-LDH with an oxygen defect show excellent electrocatalytic performance for the OER, with a low overpotential (272 mV at 10 mA/cm2), a small Tafel slope (43 mV/dec), and superior durability. Direct growth synthesis provide excellent electrical conductivity as well as strong bonding between the catalyst layer and the substrate. In addition, this synthesis process is simple to apply in the fabrication of a large size electrode and is believed to be applicable to commercialized alkaline water electrolysis.