Cs2.5H0.5PW12O40 supported on palygorskite (CsHPW/Pa) were synthesized and characterized by Fourier transform infrared spectroscopy, X-ray diffraction, and transmission electron microscopy. CsHPW inside CsHPW/Pa was retained intact Keggin anion and highly and uniformly supported on the fiber of Pa, which performed stable catalytic activity for esterification of oleic acid with ethanol. Under optimum conditions, the following amounts were reached: 20%CsHPW/Pa catalyst, 80 degrees C, 8 h, molar ratio (ethanol to oleic acid) 10:1, catalyst amount 8 wt% (in relation to the oleic acid mass), removal water agents amount 50 g/mol (basis on the oleic acid molar), and the conversion of oleic acid reached 73%.