A highly negatively charged borotungstic acid H5BW12O40 had been tested as homogeneous catalyst in esterification. Compared with common used H3PW12O40, it displayed a higher conversion (98.7%) and excellent efficiency (96.2%) due to its high amount of protons in methanol. In order to overcome the drawbacks of homogeneous heteropolyacid H5BW12O40, a Bronsted-surfactant-combined (C(16)TA)H4BW12O40 (C(16)TA = cetyltrimethyl ammonium) had been fabricated with strong acidity and nano-size micellar structure resulting in enhanced activity and stability during the reaction, which exhibited consistent activity during recycling in esterification reaction. (C) 2015 Published by Elsevier Ltd.