Electrocatalytic water oxidation requires efficient catalysts to reduce the overpotential and accelerate the sluggish kinetics of oxygen formation. Here, a promising NiFeBa material was prepared by the co-electrodeposition of Ba2+, Ni2+, and Fe3+ as an efficient catalyst for electrocatalytic water oxidation. NiFeBa showed enhanced water oxidation performance compared with NiFe layered double hydroxide and NiFe oxide, delivering a current density of 10 mA cm−2 at an overpotential of 180 mV. Doped Ba ions played a key role in stabilizing the electrogenerated Ni3+ species, producing more octahedral Ni−O structures for lattice oxygen-based water oxidation, adjusting the catalytic mechanism, and finally leading to an enhancement of catalytic efficiency.