A novel cerium MD salt of Dawson type tungstophosphoric acid (Ce2P2W18O62 center dot 16H(2)O) was prepared by doping cerous nitrate H6P2W18O62 center dot 13H(2)O powder and characterized by thermogravimetry and deifferential thermal analyses (TG/DTA), Fourier transform infrared spectroscopy (FT-IR), X-ray powder diffraction (XRD), pyridine infrared spectroscopy (Py-IR) and scanning electron microscopy (SEM). Its catalytic activity was evaluated by the probe reaction of synthesis of n-butyl acetate with acetic acid and n-butanol. The effects of various parameters such as molar ratio of n-butanol to acetic acid, reaction temperature, reaction time, and catalyst amount have been studied by single factor experiment. The results show that Ce2P2W18O62 center dot 16H(2)O behaved as an excellent heterogeneous catalyst in the synthesis of n-butyl acetate. The optimum synthetic conditions were determined as follows : molar ratio of n-butanol to acetic acid at 2.0 : 1.0, mass of the catalyst being 1.44% of the total reaction mixture, reaction temperature of 120 degrees C and reaction time of 150 min. Under above conditions, the conversion of acetic acid was above 97.8%. The selectivity of n-butyl acetate based on acetic acid was, in all cases, nearly 100%. The catalysts could be recycled and still exhibited high catalytic activity with 90.4% conversion after five cycles of reaction. It was found by means of TG-DTA and Py-IR that the catalyst deactivation was due to the adsorption of a complex of by-product on the active sites on catalysts surface or the catalyst loss in its separation from the products. Compared with using sulfuric acid as catalyst, the present procedure with Ce2P2W18O62 center dot 16H(2)O is a green productive technology due to simple process, higher yield, catalyst recycling and no corrosion for the production facilities.