Defect‐engineered　bimetallic　oxides　exhibit　high　potential　for　the　electrolysis　of　small　organic　molecules.　However,　the　ambiguity　in　the　relationship　between　the　defect　density　and　electrocatalytic　performance　makes　it　challenging　to　control　the　final　products　of　multi‐step　multi‐electron　reactions　in　such　electrocatalytic　systems.　In　this　study,　controllable　kinetics　reduction　is　used　to　maximize　the　oxygen　vacancy　density　of　a　Cu─Co　oxide　nanosheet　(CuCo2O4　NS),　which　is　used　to　catalyze　the　glycerol　electrooxidation　reaction　(GOR).　The　CuCo2O4−x　NS　with　the　highest　oxygen‐vacancy　density　(CuCo2O4−x‐2)　oxidizes　C3　molecules　to　C1　molecules　with　selectivity　of　almost　100%　and　a　Faradaic　efficiency　of　≈99%,　showing　the　best　oxidation　performance　among　all　the　modified　catalysts.　Systems　with　multiple　oxygen　vacancies　in　close　proximity　to　each　other　synergistically　facilitate　the　cleavage　of　C─C　bonds.　Density　functional　theory　calculations　confirm　the　ability　of　closely　spaced　oxygen　vacancies　to　facilitate　charge　transfer　between　the　catalyst　and　several　key　glycolic‐acid　(GCA)　intermediates　of　the　GOR　process,　thereby　facilitating　the　decomposition　of　C2　intermediates　to　C1　molecules.　This　study　reveals　qualitatively　in　tuning　the　density　of　oxygen　vacancies　for　altering　the　reaction　pathway　of　GOR　by　the　synergistic　effects　of　spatial　proximity　of　high‐density　oxygen　vacancies.