Urea　oxidation　reaction　(UOR),　an　ideal　alternative　to　oxygen　evolution　reaction　(OER),　has　received　increasing　attention　for　realizing　energy-saving　H2　production　and　relieving　pollutant　degradation.　Normally,　most　studied　Ni-based　UOR　catalysts　pre-oxidate　to　NiOOH　and　then　act　as　active　sites.　However,　the　unpredictable　transformation　of　the　catalyst＇s　structure　and　its　dissolution　and　leaching,　may　complicate　the　accuracy　of　mechanism　studies　and　limit　its　further　applications.　Herein,　a　novel　self-supported　bimetallic　Mo-Ni-C3N3S3　coordination　polymers　(Mo-NT@NF)　with　strong　metal–ligand　interactions　and　different　H2O/urea　adsorption　energy　are　prepared,　which　realize　a　bidirectional　UOR/hydrogen　evolution　reaction　(HER)　reaction　pathway.　A　series　of　Mo-NT@NF　is　prepared　through　a　one-step　mild　solvothermal　method　and　their　multivalent　metal　states　and　HER/UOR　performance　relationship　is　evaluated.　Combining　catalytic　kinetics,　in　situ　electrochemical　spectroscopic　characterization,　and　density-functional　theory　(DFT)　calculations,　a　bidirectional　catalytic　pathway　is　proposed　by　N,　S-anchored　Mo5+　and　reconstruction-free　Ni3+　sites　for　catalytic　active　center　of　HER　and　UOR,　respectively.　The　effective　anchoring　of　the　metal　sites　and　the　fast　transfer　of　the　intermediate　H*　by　N　and　S　in　the　ligand　C3N3S3H3　further　contribute　to　the　fast　kinetic　catalysis.　Ultimately,　the　coupled　HER||UOR　system　with　Mo-NT@NF　as　the　electrodes　can　achieve　energy-efficient　overall-urea　electrolysis　for　H2　production.　©　2023　Wiley-VCH　GmbH.