Portable x‐ray fluorescence (XRF) is a reliable, rapid and noninvasive technique. Recently, it has been used in a wide variety of fields where the sample must still be available after examination or when qualitative information on chemical composition is needed quickly to perform more detailed studies. These properties also make it suitable for forensic investigations, as shown by some recent reports. In the present work, a systematic evaluation of metal micro traces in electric marks was performed in a case of death by electrocution (high‐voltage current). The results are promising, as XRF has been shown to be a suitable tool not only for skin fragments but also for graphite adhesive tapes placed on the body skin areas of forensic interest and then analyzed. The latter finding proves that skin samples at autopsy are not the only valuable sampling method, thus paving the way for the application of XRF in the diagnosis of electrical injuries in living individuals as well.