The　electrochemical　urea　oxidation　reaction　(UOR)　represents　a　promising　route　to　sustainable　hydrogen　production　and　reuse　of　urea-containing　sewage.　However,　the　efficiency　of　UOR　is　hindered　by　the　dehydrogenation　of　intermediate　*CONH2NH　and　the　conversion　of　toxic　intermediate　the　*CO.　Herein,　we　report　a　robust　strategy　to　elevate　UOR　performance　by　introducing　iron　(Fe)　atoms　into　the　Ni3S2@NiSe2　heterojunctions　(denoted　Fe-Ni3S2@NiSe2).　The　Fe-Ni3S2@NiSe2　exhibits　remarkable　selectivity　and　electrocatalytic　activity　towards　UOR,　attributed　to　its　reconstruction　into　Fe-NiOOH　species　during　UOR　process,　as　confirmed　by　in-situ　Raman　technology.　Utilizing　Fe-Ni3S2@NiSe2　as　both　the　cathode　and　anode　in　a　single-chamber　electrolytic　cell,　the　hydrogen　production　rate　reaches　588.4　μmol　h−1　in　simulated　urea-containing　sewage　and　432.1　μmol　h−1　in　actual　human　urine,　respectively.　Notably,　in　both　scenarios,　no　oxygen　product　is　detected,　and　the　hydrogen　production　efficiency　surpasses　that　of　traditional　water　splitting　by　5.8-fold　and　4.3-fold,　respectively.　In-situ　infrared　spectroscopy　study　reveals　that　the　UOR　process　involves　the　cleavage　of　C-N　bond　and　the　generation　of　CO2.　Density　functional　theory　calculations　further　signifies　that　the　incorporation　of　Fe　facilitates　the　dehydrogenation　of　*CONH2NH　intermediates,　strengthens　the　d-p　hybridization,　and　weakens　O-H　bonds,　thereby　resulting　in　reduced　energy　barriers　for　UOR.　Our　strategy　holds　promise　for　efficient　hydrogen　production　from　sewage　via　UOR,　offering　potential　implications　for　wastewater　treatment　and　clean　energy　generation.　©　2024　Elsevier　B.V.