Abstract: Keggin ion based hybrid materials, [BmIm]3[PW12O40], [TBA]3PW12O40 and [BuPy]3PW12O40, were prepared by proton exchange with organic cations, 1-butyl-3-methyl imidazolium ion, tetrabutylammonium ion and butylpyridinium ion, respectively. The formation of hybrid materials was confirmed by FTIR, PXRD, SEM, TG-DTA, DSC analysis. These hybrid compounds are active for oxidation of aniline using m-chloroperbenzoic acid as an oxidant. Among the three hybrid compounds, 1-butyl-3-methyl imidazolium phosphotungstate was found to be the best and efficient catalyst for selective aniline oxidation to nitrobenzene. It is a recoverable and reusable catalytic system. The redox property of the phosphotungstate cluster in the hybrid material is involved in the catalytic activity. Graphical Abstract: [Figure not available: see fulltext.]. © 2017, Springer Science+Business Media, LLC.