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X-ray absorption near edge structure (XANES) spectroscopy was used on zoned sphalerites (ZnS) from two world-class Mississippi Valley Type deposits, the Central and Eastern Tennessee Mining district, USA, in order to investigate germanium oxidation states. Due to the low germanium concentrations of these samples, it was necessary to perform the X-ray absorption spectroscopy (XAS) in fluorescence mode. The overlapping of the Zn Kβ and Ge Kα emission lines meant that a high energy-resolution was required. This was achieved using crystal analysers and allowed a bandwidth of 1.3 eV to be obtained. Experimental spectra were compared to XANES calculations and three configurations of germanium incorporation into sphalerite were identified. The first two, the most prevalent, show germanium (II) and (IV) surrounded by sulphur atoms in tetrahedral coordination, suggesting the replacement of Zn by Ge. In the third configuration, germanium (IV) is surrounded by oxygen atoms. This third configuration is unexpected for a zinc sulphide mineral and it resembles that of argutite (GeO2).