Interfacial properties of 5 nm MgO(001)/7 nm Fe(001)/1.8 nm MgO(001)/t nm Cu-phthalocyanine (CuPc) hybrid multilayers with t = 0, 1, 7, and 10 were investigated by using x-ray photoemission spectroscopy (XPS). Rather sharp interfacial properties were observed in the CuPc films grown on an epitaxial MgO/Fe/MgO(001) trilayer than a MgO/Fe(001) bilayer. This work suggests a new way to improve device performance of organic spintronic devices by utilizing an artificially grown MgO(001) thin layer.