The　treatment　of　urea-containing　wastewater　is　crucial　for　sustainable　environmental　development,　given　its　low　theoretical　thermodynamic　barrier　(0.37　V),　which　can　effectively　replace　the　OER　process　in　water　electrolysis　and　enhance　hydrogen　production　efficiency.　Nevertheless,　designing　dual-functional　catalysts　capable　of　effectively　performing　catalytic　tasks　remains　a　challenge.　Herein,　in　this　work　a　cerium-doped　nickel　sulfide　(Ce-NiS)　catalyst　is　synthesized　by　an　electrodeposition　method,　which　is　used　as　a　bifunctional　catalyst　for　electrolytic　hydrogen　production　from　urea-containing　wastewater.　Ce-NiS　exhibits　a　higher　Faradaic　efficiency　(FE,　91.39%)　compared　to　NiS　(67.52%)　for　hydrogen　production　from　simulated　urea-containing　wastewater.　In　situ　Raman　spectroscopy　reveals　that　Ce　doping　induces　the　reconstruction　of　NiS　into　high-valence　nickel　species　(NiOOH),　which　is　considered　the　actual　active　center　for　the　electrochemical　UOR　process.　Notably,　the　apparent　electrochemical　activation　energy　for　the　UOR　decreased　from　8.72　kJ　mol−1　(NiS)　to　5.68　kJ　mol−1　(Ce-NiS),　indicating　that　doping　with　Ce　significantly　reduces　the　energy　barrier　for　the　UOR　and　enhances　the　catalytic　urea　oxidation　capability.　This　study　employs　a　strategy　of　rare-earth　metal　(Ce)　doping　to　enhance　the　efficiency　of　urea-coupled　electrolytic　hydrogen　production,　providing　promising　insights　for　energy　recovery　from　urea-containing　wastewater　and　the　development　of　high-performance　dual-functional　catalysts.　©　2024　RSC.