Iron meteorites record the evolutionary and cosmochemical processes of their parent bodies. Fe–Ni phases in iron meteorites show complex textures from various thermal histories of parent bodies as well as the phase relationships and crystal chemistry of Fe–Ni metal. Synchrotron radiation-based X-ray absorption fine structure spectra and X-ray diffraction were applied herein to the study of iron meteorite NWA 859 Fe, Ni, and Ge contents at the K-edge, since they are effective techniques in identifying crystal structures in iron meteorites. The bond distances of Fe and Ni in tetrataenite and kamacite were detected. Field-emission scanning electron microscopy and energy-dispersive spectroscopy were used to observe the petrological and chemical characteristics of the main minerals, kamacite and tetrataenite, and the trace mineral schreibersite. The tetrataenite phase and body-centered cubic kamacite formed a Widmanstätten pattern and cloudy zone. The extended X-ray absorption fine structure (EXAFS) analyses of NWA 859 and a single-crystal diffraction of tetrataenite show that it has a near-face-centered cubic (FCC) tetragonal structure with 12 nearest-neighboring Ni, Fe, and Ge atoms at distances of r_{Ni-(Ni, Fe)} = 2.5170(13) Å, r_{Fe-(Ni, Fe)} = 2.534(3) Å, and r_{Ge-(Ni, Fe)} = 2.524(5) Å, respectively. Moreover, the X-ray absorption near-edge structure (XANES) spectra suggest that the Ge in tetrataenite exhibits a specific local structure with coordination number 12, suggesting that a new local structure of Ge-(Ni, Fe) was first discovered in extraterrestrial material, forming a stable tetragonal structure at approximately 688–618 K. X-ray absorption fine structure (XAFS) is an efficient technique that could provide us further information about local atomic structures and forming conditions in extraterrestrial materials without damage.