Replacing the oxygen evolution reaction (OER) with water-assisted oxidation of organic molecules represents a promising approach for achieving sustainable electrochemical biomass utilization. Among numerous OER catalysts, spinels have received substantial attention due to their manifold compositions and valence states, yet their application in biomass conversions remains rare. Herein, a series of spinels were investigated for the selective electrooxidation of furfural and 5-hydroxymethylfurfural, two model substrates for versatile value-added chemical products. Spinel sulfides universally exhibit superior catalytic performance compared to that of spinel oxides, and further investigations show that the replacement of oxygen with sulfur led to the complete phase transition of spinel sulfides into amorphous bimetallic oxyhydroxides during electrochemical activation, serving as the active species. Excellent values of conversion rate (100%), selectivity (100%), faradaic efficiency (>95%), and stability were achieved via sulfide-derived amorphous CuCo-oxyhydroxide. Furthermore, a volcano-like correlation was established between their BEOR and OER activities based on an OER-assisted organic oxidation mechanism.