Ni-based　electrocatalysts　are　regarded　as　highly　promising　ones　for　urea-assisted　electrolytic　water　hydrogen　production　technology.　However,　during　the　urea　oxidation　reaction　(UOR)　process,　their　activity　is　significantly　constrained　by　the　unavoidable　Ni　species　self-oxidation　reaction,　and　the　harmful　liquid-phase　products　(NOx−)　generated　from　over-oxidize　urea　are　also　often　neglected.　Herein,　A　self-supported　W-doped　Ni-C3S3N3-based　coordination　polymer　electrode　(W-NT@NF)　with　tailored　Ni3+　active　sites　using　ligand　anchoring　and　high-valence　metal　doping　strategies　is　synthesized,　which　is　certified　that　this　pyrolysis-free　catalyst　achieves　dual-functional　hydrogen　evolution　reaction　(HER)　and　UOR　performance　comparable　to　reported　noble　metal/non-noble　metal　catalysts,　both　achieving　high　current　densities　approaching　1000 mA cm−2.　Density　functional　theory　(DFT)　calculations,　combined　with　spectroscopic　characterizations　that　record　the　dynamic　evolution　of　the　catalyst　during　UOR　and　oxygen　evolution　reaction　(OER)　processes,　reveal　that　the　novel　and　energetically　favorable　UOR　pathway　is　proposed,　which　initiates　directly　by　the　Ni3+　sites　without　self-oxidation　and　involve　the　participation　of　the　reconstructed　NiOOH　species　resulting　from　OER.　A　combination　of　in-line　gas　chromatography,　and　ion　chromatography　analysis　indicates　that　the　Faradaic　efficiency　(FE)　of　N2　is　higher　(34%)　at　lower　current　densities　(−2),　and　the　FE　of　NOx−　remains　below　20%　in　long-term　electrolysis.　©　2023　Wiley-VCH　GmbH.