Here we report a catalytic process for the efficient production of formic acid (FA) from common carbohydrates via VO₂⁺ formed by dissolving sodium metavanadate in acidic water. The polysaccharides undergo a hydrolysis reaction and an immediate oxidation reaction successively to produce FA in the same reaction system. The hydrolysis reaction decomposes the polymerized structures to produce monosaccharides, which are readily oxidized to FA under catalysis of VO₂⁺. Typically, formic acid mole yields are 64.9% from cellulose and 63.5% from xylan (hemicellulose). The separation of FA from the catalytic system and recycling of the catalyst are demonstrated.