Electrochemical valorization of biomass waste (e.g., glycerol) for production of value-added products (such as formic acid) in parallel with hydrogen production holds great potential for developing renewable and clean energy sources. Here, a synergistic effort between theoretical calculations at the atomic level and experiments to predict and validate a promising oxide catalyst for the glycerol oxidation reaction (GOR) are reported, providing a good example of designing novel, cost-effective, and highly efficient electrocatalysts for producing value-added products at the anode and high-purity hydrogen at the cathode. The predicted CoMoO4 catalyst is experimentally validated as a suitable catalyst for GOR and found to perform best among the investigated metal (Mn, Co, Ni) molybdate counterparts. The potential required to reach 10 mA cm−2 is 1.105 V at 60 °C in an electrolyte of 1.0 m KOH with 0.1 m glycerol, which is 314 mV lower than for oxygen evolution. The GOR reaction pathway and mechanism based on this CoMoO4 catalyst are revealed by high-performance liquid chromatography and in situ Raman analysis. The coupled quantitative analysis indicates that the CoMoO4 catalyst is highly active toward C-C cleavage, thus presenting a high selectivity (92%) and Faradaic efficiency (90%) for formate production.