Electrocution cases reported in the literature were mainly caused by low-voltage alternating current, with few cases associated with high-voltage direct current. In this article, we report the case of a 48-year-old woman who unexpectedly and suddenly died in the wild because of electric shock by a high-voltage direct current while hunting. The postmortem inspection found a suspected current mark on her right upper thigh, and histological examination of the suspected current mark revealed a slight elongation of the epidermal cell nuclei and separation of the corneous layer. Metal elements analysis by microbeam x-ray fluorescence spectrometry demonstrated a peak concentration of iron in the suspected current-injured skin surface, which was in line with the metal wire at the scene. In addition, the deceased had coronary atherosclerotic heart disease, which can increase the body's risk to the current damage. Our results indicated the usefulness of microbeam x-ray fluorescence spectrometry for the forensic diagnosis of electrocution.