Ruthenium (Ru)‐ and iridium (Ir)‐based nanomaterials have always been regarded as efficient electrocatalysts for oxygen evolution reaction (OER) in acidic electrolytes. Herein, we develop a facile dodecylamine‐assisted hydrothermal synthesis for producing carbon‐supported IrRu alloy nanoparticles with controllable Ir/Ru ratios and ultrafine sizes towards high‐efficiency OER and overall water electrolysis. In this strategy, the dodecylamine that serves as a capping and reducing agent enables the final IrRu alloy nanoparticles to possess average sizes < 3 nm and high degree of dispersion on carbon substrate. By combining high OER activity of Ru with high acidic robustness of Ir, the as‐prepared IrRu/C nanoparticles at a suitable Ir/Ru ratio of 1/3 show good activity and durability for the OER electrocatalysis and overall water splitting. In specific, the Ir1Ru3/C catalyst exhibits the lowest overpotential of 302 mV at the current density of 10 mA cm‐2 and the highest mass activity of 120.5 mA mg‐1 at 1.532 V for OER in 0.5 M H2SO4 electrolyte. In addition, a two‐electrode acidic electrolyzer assembled with Ir1Ru3/C at anode and commercial Pt/C at cathode (Pt/C|| Ir1Ru3/C) exhibits a low cell voltage of 1.44 V for achieving the current density of 10 mA cm‐2, along with a satisfied 20‐h durability.