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Functionalized ionic liquid samples (bmim-PW12) were synthesized by 1-butyl-3-methyl-imidazolium bromide (bmimBr) and 12-phosphotungstic heteropolyacid (PW12). The samples were annealed at 100–450°C and were characterized by Fourier transform infrared spectroscopy, X-ray diffraction, scanning electron microscope, thermal gravity-DTG, brunauer emmett teller, and NH3-temperature programmed desorption. The results showed that the bmim-PW12 samples were crystal and maintained intact Keggin structure. The organic parts of those samples were partly decomposed at a temperature more than 350°C. The sample annealed at 400°C exhibited nano-porous structure, strong acidity, and excellent catalytic activity on the esterification of n-butanol with acetic acid. The higher ester yield was obtained when the mass ratio of catalyst over the reactants amount was 5% for bmim-PW12 catalyst annealed at 400°C.