Abstract: Using the synthesized molybdenum-vanadium homopolyacid Na₆α-Mo₆V₂O₂₆·16H₂O as catalyst and p-toluene sulfonic acid as acid catalyst, the catalytic performance of the molybdenum-vanadium homopolyacid for the selective conversion of cellulose to formic acid(FA) was investigated under aqueous medium and O₂ atmosphere. The experimental results showed that the synthesized molybdenum-vanadium homopolyacid exhibited strong oxidizing property. Under the conditions of 0.2 g of cellulose, 0.1 g of Na₆α-Mo₆V₂O₂₆·16H₂O, 0.15 g of p-toluene sulfonic acid, 10 mL of deionized water, O₂ pressure of 1 MPa, and temperature of 140 ℃ were reacted for 3 h, the conversion rate of cellulose reached 98%, and the yield of formic acid was 47%. In addition, catalytic performance of the catalyst for the conversion of monosaccharides(xylose and glucose) into formic acid was studied, and the conversion of xylose to formic acid had the highest yield of 63%.