Glycerol electrooxidation (GOR), as an innovative strategy for the production of value-added chemicals, is considered a promising anodic alternative to oxygen evolution reaction in electrocatalysis. However, the high potential and the limited selectivity and faradaic efficiency impede the industrial-scale application toward GOR. Herein, we for the first time constructed rhenium and ruthenium co-doped transition metal alloy (NiCoFeRuRe) for the efficient electrooxidation of glycerol to formate. Benefiting from the rapid generation of M3+-OOH induced by Ru element and the inhibition of OER and excessive oxidation of glycerol by Re species through in situ chacterization, the optimized NiCoFeRuRe requires only 1.133 VRHE to achieve a current density of 10 mA cm-2, a faradaic efficiency of 95.6% for formate product with a stability more than 450 h. Importantly, employing NiCoFeRuRe as a bifunctional catalyst, the cell is constructed to produce hydrogen and formate simultaneously, which is 265 mV lower than the electrolytic water splitting owning an excellent stability of 350 h. This work provides a facile strategy for rationally designing high-performance GOR catalysts for biomass upgradings.