The depth sensitivity provided by the different penetration ranges of conversion electron and conversion X‐ray Mössbauer spectroscopy (CEMS and CXMS) is used to distinguish the information obtained from the compound and diffusion layers at the surface of plasma nitrocarburized pure iron. CEMS, for its part, shows that the 12 μm compound layer consists mainly of the ϵ‐phase (nitride/carbonitride) and θ‐cementite in addition to a very small amount of α‐ferrite, while the diffusion layer consists of ferrite. The results of X‐ray diffraction are in good agreement with the Mössbauer results. CXMS, on the other hand, shows a contribution of ferrite to the total area under the Mössbauer spectrum of about 26%. This means that the depth of origin of the CXMS information must be greater than the thickness of the compound layer. This being unexpected, a new estimation of the information depth is attempted. The maximum depth of origin of the CXMS information for the magnetically split spectra is found to be about 30 to 50 μm.