In electrochemical energy storage and conversion systems, the anodic oxygen evolution reaction (OER) accounts for a large proportion of the energy consumption. The electrocatalytic urea oxidation reaction (UOR) is one of the promising alternatives to OER, owing to its low thermodynamic potential. However, owing to the sluggish UOR kinetics, its potential in practical use has not been unlocked. Herein, we developed a tungsten‐doped nickel catalyst (Ni‐WO_x) with superior activity towards UOR. The Ni‐WO_x catalyst exhibited record fast reaction kinetics (440 mA cm⁻² at 1.6 V versus reversible hydrogen electrode) and a high turnover frequency of 0.11 s⁻¹, which is 4.8 times higher than that without W dopants. In further experiments, we found that the W dopant regulated the local charge distribution of Ni atoms, leading to the formation of Ni³⁺ sites with superior activity and thus accelerating the interfacial catalytic reaction. Moreover, when we integrated Ni‐WO_x into a CO₂ flow electrolyzer, the cell voltage is reduced to 2.16 V accompanying with ≈98 % Faradaic efficiency towards carbon monoxide.