We studied the Co/Fe bi- and multilayer growth on Fe single crystal using the primary-beam diffraction modulated electron emission (PDMEE) technique. This approach enables a chemical selected structural characterization of both surface and buried layers and interfaces to be performed. Co growth on the Fe(001) surface was studied in the 3\u201370 ML coverage range. The transition from the initial epitaxial bcc phase of the Co film to the stable hcp phase was found to occur rather abruptly at 25\u201330 ML coverage, a value larger than previously reported in the literature. Subsequent Fe deposition on the Co hcp film recovers the bcc structure in the sandwiched Co layer. However, removal of the Fe epilayer by mild sputtering results again in ...