The “shell biorefinery,” which valorizes the shell waste chitin into fine chemicals, has developed rapidly in recent years. Herein, we present a novel base-free heteropolyacid-catalyzed oxidation method for the transformation of chitin biomass into organic acid. After a series of optimization experiments, a 5.93 % yield of formic acid and 25.09 % yield of acetic acid were achieved in the presence of 0.5 equivalent of Mo-V-P heteropolyacids (H4PMo11VO40·2H2O) and air at 180 °C under hydrothermal conditions for 4 h. Meanwhile, we have demonstrated that the Keggin-type heteropolyacid catalysts are capable of efficiently converting microcrystalline chitin into organic acids. The synthesized heteropolyacids are well characterized with FT-IR, XRD, ICP-AES, and TGA. The possible reaction pathway was speculated accordingly. This method offers several advantages, including readily available raw materials, simple operation, and relatively higher yield.