A new economic and green route to synthesize phthalide from 1,2-benzenedimethanol using aqueous hydrogen peroxide as the oxidant and tungstic acid as the catalyst under organic solvent-free conditions is presented. This process proceeds with advantages from the viewpoint of green chemistry, in which the only by-product of H₂O₂ is water and the catalyst can also be easily recovered. The desired product with high purity and good yield can be conveniently obtained when cooled after reaction.