A series of phosphotungstic acid pillared Zn-Ti hydrotalcites(LDHs) were prepared by using the ion-exchange method. The structures of samples were characterized by XRD、FT-IR、SEM. The results showed that no significant structural change of LDH was observed after intercalation. The epoxidation of fatty acid methyl ester reactions were carried out over the catalyst samples. It was found that, 90.6% conversion of fatty acid methyl ester and 86.0% selectivity to epoxidation product could be obtained at the reaction temperature 70 ℃, reaction time 7 h, n(H2O2):n(double bond)=1.5:1, and catalyst dosage 7.0% (based on the weight of fatty acid methyl ester). The catalytic performance of phosphotungstic acid pillared Zn-Ti hydrotalcites was better than that of Zn-Ti LDH respectively. The novel phosphotungstic acid pillared Zn-Ti hydrotalcites catalysts revealed good catalytic performances to epoxidation of fatty acid methyl ester reactions. Furthermore, the pillared hydrotalcites showed a good repeatability after 5 times reuse.