AbstractHistorical heritage pieces allow a better comprehension of the characteristics of different civilizations over time. The characterization of such pieces is of paramount importance for their preservation. Energy‐dispersive X‐ray fluorescence (EDXRF) is recommended for this application, mostly because it is non‐destructive and the equipment is portable. However, one of its limitations is the difficulty in separating the signal from the substrate and the coating of multilayered samples, as it does not provide depth resolution. This project investigates the application of EDXRF in the characterization of metallic coatings, in the context of historical heritage. The elemental concentration of electrodeposited Ni coatings onto carbon steel substrates was obtained from EDXRF analyses. The relationship between the layer thickness and the variation of the Kα/Kβ intensity ratio of nickel peaks was exploited and the thicknesses of the coatings were estimated through EDXRF measurements. For comparison, particle‐induced x‐ray emission spectroscopy and scanning electron microscopy of the cross‐section were employed, providing a depth profile of the coatings. The estimated thicknesses from EDXRF analysis were comparable to those observed in the microscopy images for thinner films (up to 8 μm). On the other hand, for thicker films, the thicknesses were underestimated, due to the technique's depth limit and matrix effects, as secondary absorption. Despite these limitations, EDXRF remains valuable for evaluating cultural heritage pieces, often providing sufficient information to address authenticity concerns or to guide restoration processes. A case study was also performed to apply the methodology discussed on historical metallic pieces.