NiFe oxyhydroxides, generally reconstructed on surface during oxygen evolution reaction (OER), are real active species for water oxidation; however, their direct and convenient preparation remains challenging. Here, we develop a one-step approach to prepare biphase (α/δ) Ni-doped FeOOH catalyst in 3 min under room temperature. The core of this ultrafast method is that Fe2+ derived from the redox reaction of Fe3+ and Ni2+ accelerate Fenton-like reaction, while simultaneously producing mixed-valence Ni ions(Ni2+, Ni3+) results in not only homovalent and heterovalent doping, but also biphase Ni-doped FeOOH heterojunction with high and low crystallinity. Specifically, Ni2+ doping leads to a preferred formation of low-crystalline δ-oriented Ni-doped FeOOH with abundant oxygen vacancies, which is in favor of triggering the lattice oxygen mechanism (LOM) during OER. Benefitting from high/low crystalline biphase heterojunction and LOM, the optimized Ni-FeOOH merely needs low overpotential of 300 mV to reach 1000 mA cm−2 for OER in alkaline electrolyte and also shows excellent durability even at a high current density of 500 mA cm−2. This work provides a cost-effective strategy to fabricate highly active and robust non-noble electrocatalysts that can potentially be applied for industrial-scale OER electrolysis.