Due to the increasing global demand for pure silver, native wire silver aggregates in very high purities are gaining more industrial attention. Up to the present, no substantial metallurgical investigation of natural wire silver exists in the accessible literature. To convey urgently needed cross-disciplinary fundamental knowledge for geoscientists and metallurgical engineers, twenty natural wire silver specimens from eight different ore deposits have been investigated in detail for the first time by EBSD (Electron Back Scattering Diffraction), supported by light microscopy and micro-probe analyses. The improved understanding of the natural silver wire microstructure provides additional information regarding the growth of natural silver aggregates in comparison to undesired artificial growth on electronic devices. Clear evidence is provided that natural silver curls and hairs exhibit a polycrystalline face-centered cubic microstructure associated with significant twinning. Although the investigated natural wire silver samples have relatively high purity (Ag > 99.7 wt.-%), they contain a variety of trace elements such as, S, Cu, Mn, Ni, Zn, Co and Bi, As and Sb. Additionally, Vickers micro-hardness measurements are provided for the first time which revealed that natural silver wires and curls are softer than it might be expected from conversion of the general Mohs hardness of 2.7.