The MIL-100(Cr), PW12@MIL-100(Cr) and PW4@MIL-100(Cr) catalysts were prepared and characterized through XRD, FTIR, BET, SEM, EDS and Raman spectroscopy. A comparison of the catalytic properties of the synthesized materials in the epoxidation of FAMEs with hydrogen peroxide was made. The PW4@MIL-100(Cr) catalyst exhibited the highest catalytic activity and provided a high selectivity for the formation of epoxides. The effects of the reaction temperature, catalyst loading, reaction time and FAME:hydrogen peroxide molar ratio on the reaction performance were investigated, and the optimal process conditions were determined. An epoxide yield of 73% with a selectivity of 77% could be obtained using PW4@MIL-100(Cr) after 4 h at 40 °C. The catalytic stability test showed that PW4@MIL-100(Cr) could be easily separated and reused without any treatment for at least five consecutive cycles without a loss of activity or selectivity.