The stability of anode electrode has been a primary obstacle for the oxygen evolution reaction (OER) in acid media. We design Ir-oxygen of hydroxyl-rich blue TiO2 through covalent bonds (Ir–O2–2Ti) and investigate the outcome of favored exposure of different amounts of covalent Ir–oxygen linked to the conductive blue TiO2 in the acidic OER. The Ir-oxygen-blue TiO2 nanoclusters show a strong synergy in terms of improved conductivity and tiny amount usage of Ir by using blue TiO2 supporter, and enhanced stability using covalent Ir-oxygen-linking (i.e., Ir oxide) in acid media, leading to high acidic OER performance with a current density of 10 mA cm−2 at an overpotential of 342 mV, which is much higher than that of IrO2 at 438 mV in 0.1 M HClO4 electrolyte. Notably, the Ir–O2–2Ti has a great mass activity of 1.38 A/mgIr at an overpotential 350 mV, which is almost 27 times higher than the mass activity of IrO2 at the same overpotential. Therefore, our work provides some insight into non-costly, highly enhanced, and stable electrocatalysts for the OER in acid media.