In this work,a series of trimetal Prussian blue analogues had been synthesized by adding Fe and Cu element to the five types bimetallic Prussian blue analogues,FeCoPBA,CdCoPBA,CoCoPBA,MnCoPBA,ZnCoPBA,respectively.And they were used as heterogeneous catalysts to study the catalytic effects of epoxidation of styrene.The results reveal that the catalytic effects of trimetal Prussian blue analogues with Fe or Cu element were better than that of bimetallic Prussian blue analogues.And these PBAs genarally have smaller particle sizes and weaker diffraction peaks than corresponding bimetallic Prussian blue analogues by scanning electron microscopy(SEM),infrared spectroscopy(IR),X-ray diffraction(XRD)measurement.Then,we selected CuZnCo PBA and CuCdCo PBA for further study by a variety of testing.And their thermodynamic data were obtained by isothermal titration calorimetry.The results indicate that the synthesis of CuZnCo PBA and CuCdCo PBA is a spontaneous exothermic process and the enthalpy change of synthesis process of CuZnCo PBA and CuCdCo PBA are between the corresponding bimetallic PBAs.