Urea oxidation reaction (UOR) has been utilized to substitute the oxygen evolution reaction (OER), to escalate the energy conversion efficiency in electrochemical hydrogen generation processes with denitrification of widespread urea in wastewater. This study reports breakthroughs in Ni-based UOR electrocatalysts, particularly with NiFe oxalate (O-NFF), derived from Ni3Fe alloy foam with prismatic nanostructures and elevated surface area. The O-NFF achieves cutting-edge performances, representing 500 mA cm−2 of current density at 1.47 V RHE and exceptionally low Tafel slope of 12.1 mV dec−1 (in 1 m KOH with 0.33 m urea). X-ray photoelectron/absorption spectroscopy (XPS/XAS) coupled with density functional theory calculations unveil that oxalate ligands induce charge deficient Ni center, promoting stable urea-O adsorption. Furthermore, Fe dopants enhance oxalate-O charge density and H-bond strength, facilitating C-N cleavage for N2 and NO2− formation. The extraordinary UOR kinetics by the tandem effects of oxalate and Fe prevent Ni over-oxidation, corroborated by operando XAS, minimizing OER interference. It agrees with an adaptive reconstruction to Fe-doped β-NiOOH on top surface in extended urea electrolysis with marginal loss in UOR kinetics. This findings shed light to bimetal-organic-framework as (pre)catalysts to improve industrial electrolytic H2 production.​