A generalized synthesis method for decatungstate hybrids from bisulfate-based acidic ionic liquids was reported. N-butylpyridinium decatungstate [bPy](4)W10O32 and 1-butyl-3-methylimidazolium decatungstate [bmIm](4)W10O32 were synthesized and have been demonstrated to be good thermo-regulated phase transfer catalysts in an organic-solvent-free selective oxidation of alcohols under mild conditions. Advantages of heterogeneous and homogeneous catalysis are combined here, provided good self-separated and ease-of-recycling catalysts.