Thin films (50nm) of Fe 100−x Pd x and Fe 100−x Mn x (x=20 and 50) were deposited by laser ablation on a Si wafer and studied by X-ray diffraction (XRD) and conversion electron Mössbauer spectroscopy (CEMS). In all cases, the XRD patterns of the target surface before and after ablation show a congruent transfer of ablated material. For the Fe 80 Pd 20 thin film, XRD spectra show the formation of FePd, iron, Pd oxide and traces of hematite in the ablated film. Complementary information obtained by CEMS indicates the presence of an upper 50-nm thick surface layer of hematite in the deposited film. Fe 50 Pd 50 phase was observed by CEMS and a Pd oxide component was identified by XRD, along with traces of hematite. In the case of Fe 80 Mn 20 , the CEMS spectrum is consistent with the occurrence of the antiferromagnetic FeMn phase and the XRD pattern also shows the presence of Fe in the structure. For the system Fe 50 Mn 50 , we obtain by CEMS an antiferromagnetic phase of FeMn and by XRD we trace the presence of nanohematite and in-depth iron. For x=20 in both iron-rich systems investigated, we observe the segregation of iron with subsequent conversion to hematite. The study shows that the stoichiometry of the compounds plays a decisive role in determining their structural and magnetic properties.