A highly active and selective heterogeneous catalyst consisting of Fe–Mn double metal cyanide is reported for the transesterification of cyclic carbonates with methanol. Fe–Mn double metal cyanide complex with a Fe/Mn metal ratio of 8 was found to provide significantly higher TOF and stability for transesterification of propylene carbonate with methanol to dimethyl carbonate. The experimental results showed that Mn content has a significant influence on the catalytic activity. TEM and XRD analyses suggested that Fe–Mn complex represents a cubic crystalline structure. XPS analysis showed that all Fe exists in Fe2+ state. However, for the Mn element, 86.8% of Mn exists in Mn2+ state with only 13.2% in Mn4+ state. Furthermore, FTIR and DRIFT UV–vis results verified the formation of a new mixed-metal complex of ferrocyanide moiety and Mn ions via bridging cyanide ligands. NH3-TPD results showed that Fe–Mn double metal cyanide has a strong acidity, which correlates to the high activity of Fe–Mn double metal cy...