With silica-cerous of high activity as catalyst, ethylene glycol ethyl ether acetate was synthesized from ethylene glycol ethyl ether and acetic acid. The proper conditions for the synthesis were obtained by a single factor experiment and orthogonal experiment. Based on 0.3 mol acetic acid, the optimum conditions were as follows: the mass ratio of silica-cerous (15% loaded sulfate cerous) / acetic acid being 0.056 : 1, the mol ratio of acetic acid / ethylene glycol ethyl ether being1 : 1.2, the amount of cyclohexane being 30 mL, reaction temperature being 90 °C, and reaction time being 2 h. Such optimal conditions give the highest yield of 99.53 % and selectivity of 100 % of ethylene glycol ethyl ether acetate. Its structure was confirmed by IR, and the catalyst still has high activity after being reused for five times.