Synchrotron-based microscale X-ray absorption near edge structure spectroscopy (μ-XANES) has been combined with X-ray fluorescence (μ-XRF) mapping to investigate Ge, Cu and Fe oxidation states in compositionally zoned Ge-rich sphalerite from the Saint-Salvy deposit (France). The present study aims at improving our understanding of substitution mechanisms and trace element uptake relative to Ge isotope fractionation in sphalerite. K-Edge XANES records of various Ge-, Cu- and Fe-bearing sulphides are presented for comparison with sphalerite, and ab initio calculations at the Ge K-edge complete our experimental data. The Ge K-edge spectra of the Ge-bearing sphalerite are identical to those of germanite, renierite and briartite, indicating the presence of tetrahedrally-coordinated Ge4+. In addition, Cu and Fe K-edge spectra suggest the presence of Cu+ and Fe2+, respectively, in the tetrahedral site. No significant differences in the oxidation states of Ge, Cu and Fe were observed within or between the zoning types or between the samples. The intake of Ge4+ in sphalerite may therefore occur in the tetrahedral divalent metal site via coupled substitutions charge-balanced by monovalent elements such as 3Zn2+ ↔ Ge4+ + 2Cu+, resulting in a strong Ge–Cu elemental correlation, or, when Ge does not correlate with monovalent elements, through the creation of lattice vacancies such as 2Zn2+ ↔ Ge4+ + □ (vacancy). The tetravalent state of Ge is compatible with temperature-related Ge isotopic fractionation and can explain the large range of δ74Ge measured in the Saint-Salvy sphalerite. Moreover, the exceptional enrichment in Ge and the large variations in the ‘bulk’ Ge contents in these sphalerites do not appear to be related to charge effects but would instead result from the effect of temperature-related partitioning.