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Hydrogen production by electrocatalytic water splitting is an efficient and economical technology, however, is severely impeded by the kinetic-sluggish and low value-added anodic oxygen evolution reaction. Here we report the nickel-molybdenum-nitride nanoplates loaded on carbon fiber cloth (Ni-Mo-N/CFC), for the concurrent electrolytic productions of high-purity hydrogen at the cathode and value-added formate at the anode in low-cost alkaline glycerol solutions. Especially, when equipped with Ni-Mo-N/CFC at both anode and cathode, the established electrolyzer requires as low as 1.36 V of cell voltage to achieve 10 mA cm
, which is 260 mV lower than that in alkaline aqueous solution. Moreover, high Faraday efficiencies of 99.7% for H
evolution and 95.0% for formate production have been obtained. Based on the excellent electrochemical performances of Ni-Mo-N/CFC, electrolytic H
and formate productions from the alkaline glycerol solutions are an energy-efficient and promising technology for the renewable and clean energy supply in the future.