Four kinds of dectungstates such as (C₅H₅NC₁₆H₃₃)₄W₁₀O₃₂(I), [(CH₃)₃NC₁₆H₃₃]₄W₁₀O₃₂(II), [(CH₃)₃NC₁₈H₃₇]₄W₁₀O₃₂(III), [C₆H₅CH₂N(C₂H₅)₃]₄W₁₀O₃₂(IV) have been synthesized and characterized by element analysis, TG-DSC, IR and UV-Vis. Their catalytic properties in oxidation of cyclohexene, cyclohexanol, cyclohexanone and 1, 2-cyclohexanediol to adipic acid were investigated with aqueous 30% H₂O₂. The results show (C₅H₅NC₁₆H₃₃)₄W₁₀O₃₂(I) catalyst exhibits best activity in four kinds of cations. Moreover, the larger of the single carbon chain of quaternary ammonium dectungtates, the better activity of the catalysts exhibit. Adipic acid can be obtained in 84.5% yield when the mixture of cyclohexene, 30(wt.)% H₂O₂ and catalyst I (in mol ratio of 100:538:0.6) was stirred vigorously at 90^oC for 20 h. The catalytic system was carried out without organic solvent and halogen conditions in an economically, technically, and environmentally satisfying manner. So the oxidation procedures meet the needs of contemporary green chemistry and suitable for practical organic synthesis.