By　substituting　the　oxygen　evolution　reaction　(OER)　with　the　anodic　urea　oxidation　reaction　(UOR),　it　not　only　reduces　energy　consumption　for　green　hydrogen　generation　but　also　allows　purification　of　urea-rich　wastewater.　Spin　engineering　of　the　d　orbital　and　oxygen-containing　adsorbates　has　been　recognized　as　an　effective　pathway　for　enhancing　the　performance　of　electrocatalysts.　In　this　work,　we　report　the　fabrication　of　a　bifunctional　electrocatalyst　composed　of　amorphous　RuO2-coated　NiO　ultrathin　nanosheets　(a-RuO2/NiO)　with　abundant　amorphous/crystalline　interfaces　for　hydrogen　evolution　reaction　(HER)　and　UOR.　Impressively,　only　1.372　V　of　voltage　is　required　to　attain　a　current　density　of　10　mA　cm(-2)　over　a　urea　electrolyzer.　The　increased　oxygen　vacancies　in　a-RuO2/NiO　by　incorporation　of　amorphous　RuO2　enhance　the　total　magnetization　and　entail　numerous　spin-polarized　electrons　during　the　reaction,　which　speeds　up　the　UOR　reaction　kinetics.　The　density　functional　theory　study　reveals　that　the　amorphous/crystalline　interfaces　promote　charge-carrier　transfer,　and　the　tailored　d-band　center　endows　the　optimized　adsorption　of　oxygen-generated　intermediates.　This　kind　of　oxygen　vacancy　induced　spin-polarized　electrons　toward　boosting　HER　and　UOR　kinetics　and　provides　a　reliable　reference　for　exploration　of　advanced　electrocatalysts.