Electrochemical　glycerol　oxidation　features　an　attractive　approach　of　converting　bulk　chemicals　into　high-value　products　such　as　glyceric　acid.　Nonetheless,　to　date,　the　major　product　selectivity　has　mostly　been　limited　as　low-value　C-1　products　such　as　formate,　CO,　and　CO2,　due　to　the　fast　cleavage　of　carbon-carbon　(C-C)　bonds　during　electro-oxidation.　Herein,　the　study　develops　an　atomically　ordered　Ni3Sn　intermetallic　compound　catalyst,　in　which　Sn　atoms　with　low　carbon-binding　and　high　oxygen-binding　capability　allow　to　tune　the　adsorption　of　glycerol　oxidation　intermediates　from　multi-valent　carbon　binding　to　mono-valent　carbon　binding,　as　well　as　enhance　*OH　binding　and　subsequent　nucleophilic　attack.　The　Ni3Sn　electrocatalyst　exhibits　one　of　the　highest　glycerol-to-glyceric　acid　performances,　including　a　high　glycerol　conversion　rate　(1199　mu　mol　h(-1))　and　glyceric　acid　selectivity　(62　+/-　3%),　a　long　electrochemical　stability　of　＞　150　h,　and　the　capability　of　direct　conversion　of　crude　glycerol　(85%　purity)　into　glyceric　acid.　The　work　features　the　rational　design　of　highly　ordered　catalytic　sites　for　tailoring　intermediate　binding　and　reaction　pathways,　thereby　facilitating　the　efficient　production　of　high-value　chemical　products.