Electrocatalytic water oxidation is a rate-determining step in the water splitting process; however, its efficiency is significantly hampered by the limitations of cost-effective electrocatalysts. Here, an advanced Co(OH)2 electrocatalyst with ultralow iridium (Ir) doping is developed to enable outstanding oxygen evolution reaction (OER) properties; that is, in a 1 M KOH medium, an overpotential of only 262 mV is required to achieve a current density of 10 mA cm-2, and a small Tafel slope of 66.9 mV dec-1 is achieved, which is markedly superior to that of the commercial IrO2 catalyst (301 mV@10 mA cm-2; 66.9 mV dec-1). Through the combination of experimental data and a mechanism study, it is disclosed that the high intrinsic OER activity results from the synergistic electron coupling of oxidized Ir and Co(OH)2, which significantly moderate the adsorption energy of the intermediates. Moreover, we have also synthesized Ru-Co(OH)2 nanosheets and demonstrated the universal syntheses of Ir-doped CoM (M = Ni, Fe, Mn, and Zn) layered double hydroxides (LDHs).