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).