Three kinds of peroxotungstates complexes such as (C₅H₅NC₁₆H₃₃)₂W₂O₃(O₂)₄, [(CH₃)₃NC₁₆H₃₃]₂W₂O₃(O₂)₄, [(C₇H₇NC₁₂H₂₅(CH₃)₂]₂W₂O₃(O₂)₄, had been synthesized and characterized by elemental analysis, IR, TG-DSC and UV-Vis. Their catalytic properties in oxidation of benzyl alcohol to benzaldehyde by aqueous 30(wt.) % H₂O₂ were investigated with ionic liquids such as [bmim]BF₄, [bmim]PF₆ or [omim]BF₄ as a solvent. The results show (C₅H₅NC₁₆H₃₃)₂W₂O₃(O₂)₄ catalyst exhibits best activity in above catalysts. The oxidation of benzyl alcohol (10 mmol) with 30% H₂O₂ (11 mmol) catalyzed by (C₅H₅NC₁₆H₃₃)₂W₂O₃(O₂)₄ (0.1 mmol) in [bmim]BF₄ at 90^oC  for 3 h gave 68% yield of benzaldehyde, we found that the reaction system became a homogeneous solution when ionic liquid [bmim]BF₄ was added to the oil-water biphasic system, and turned to biphasic systems again after completion of the reaction, which make the separation of product more convenient. In addition, Benzaldehyde can be obtained in 58% yield and 34% in [bmim]PF₆ and [omim]BF₄, respectively.