The burials of famous Xiongnu people are a unique source of information about Xiongnu culture, due to the variety of organic findings. SRXRF analysis of hair, clay, bones, teeth and woollen cloth was carried out. An anomalously high copper content was observed in all hair samples, whereas the levels of copper in bone and clay were low. To define the hair morphology and the elemental distribution in the hair cross-section, high-resolution X-ray computed tomography (HRXCT) and energy-dispersive spectroscopy (EDS) with scanning electron microscopy (SEM) were used. The X-ray absorption fine-structure method (XAFS) was applied to determine the local copper environment. The majority of the copper species in the hair and enamel samples are present as Cu2+ cations in a distorted octahedral (4+2) coordination, surrounded by light ligands (oxygen/nitrogen). A similar distorted octahedral coordination is typical for both inorganic mixed oxide/hydroxide Cu nanosystems and metal-organic Cu complexes (with oxygen/nitrogen).