Urea　oxidation　reaction　(UOR)　kinetics　is　severely　limited　by　suboptimal　intermediate　adsorption,　which　can　be　significantly　improved　by　modulating　catalyst　spin　configurations.　Herein,　we　report　an　effective　strategy　for　reforming　the　Ru　spin　configuration　in　pyrochlore　oxide　Y2Ru2O7　(YRO)　to　enhance　UOR　performance　through　gradient　orbital　coupling.　By　partially　substituting　Y　with　Sm,　we　precisely　regulate　the　electronic　structure　of　candidate　Y1.9Sm0.1Ru2O7　(YRO-Sm),　transforming　Ru　spin　configuration　from　the　low　spin　to　the　high　spin　(HS)　configuration.　The　HS　configuration　endows　YRO-Sm　with　excellent　UOR　activity　(1.43　V　at　j　=　100　mA　cm−2)　and　robust　stability.　Theoretical　analysis　reveals　that　Sm　substitution　leads　to　a　significant　Sm(4　f)–O(2p)–Ru(4d)　orbital　electron　coupling　effect.　The　highly　degenerate　4　f　orbitals　of　Sm　enhance　Ru–O　covalency　and　Ru　electron　localization　in　YRO-Sm,　facilitating　*COO　intermediate　dissociation　and　thereby　lowering　the　energy　barrier　for　UOR.　The　practical　potential　of　YRO-Sm　was　further　demonstrated　through　its　successful　integration　into　both　a　hybrid　water　electrolyzer　for　energy-saving　hydrogen　production　and　a　urea-assisted　zinc–air　battery.　This　work　demonstrates　a　promising　pathway　for　developing　high-performance　pyrochlore　catalysts　via　spin　state　engineering　for　sustainable　energy　conversion　applications.　©　2025　Elsevier　B.V.