Heteropolyacids (HPAs) which are freely soluble in H2O could be made insoluble solid acid by supporting onto suitable supports. The supported HPAs thus obtained catalyzed the water participating reaction of esterification more efficiently. A series of the solid acid catalyst containing 20-70% of heteropolyacid, 12-tungstophosphoricacid, supported onto neutral alumina was synthesized. All amorphous materials were characterized by chemical stability, ion exchange capacity, TGA, DSC, FT-IR, XRD and surface area measurement (Brunner-Enimett-Teller (BET) method). The above studies indicate the increase in the stability of 12-tungstophosphoricacid after supporting onto support and the supported structure does not get destructed. The catalytic activity of these materials was evaluated by carrying out liquid phase esterification of 1degrees alcohol (n-butanol) and 2degrees alcohol (cyclohexanol). Based on the above experimental findings, catalytic performance was optimised with a loading of 30% 12-tungstophosphoricacid onto neutral alumina (AH(3)). AH(3) was calcinated at 300 and 500degreesC, designated as AH(33) and AH(35) and characterized for FT-IR and DRS. FT-IR and DRS studies indicate that the 12-tungstophosphoricacid keeps its Keggin type structure unaltered up to 500degreesC when supported onto neutral alumina. Total acidity of AH(3), AH(33) and AH(35) was determined by chemisorption of ammonia. The particle size distribution for the three mentioned samples was also studied. The catalytic activity of AH(33) and AH(35) was examined by carrying out same esterification reactions under same conditions. The results indicate that the catalyst containing 30% 12-tungstophosphoricacid and calcinated at 500degreesC (AH(35)) is the best. (C) 2004 Elsevier B.V. All rights reserved.