This paper reports the facile synthesis of vanadium phosphate (VPO) by the decomposition of VOHPO4 center dot 0.5H(2)O which was prepared by reduction of dihydrate VOPO4 center dot 2H(2)O with isobutanol. The material was promoted with aluminum by impregnation method. The catalysts were unambiguously characterized by N-2 adsorption-desorption, XRD, FT-IR techniques, UV-Vis DRS and the total amount of the acidity of the catalysts was estimated by NH3-TPD. The catalytic activities were checked in the heterogeneous catalytic esterification of acetic acid with 1A degrees alcohol (n-butanol) in a solvent free medium. The optimization of reaction was carried out by varying temperature from 75 to 150 A degrees C, molar ratio (butanol:acetic acid) from 1:1 to 1:4. Under optimum conditions, the catalytic esterification runs revealed a significant effect of the VPO giving 62% conversion with 100% selectivity to butyl acetate.