X-ray absorption spectroscopy was used to study the microscopic origin of conductance and resistive switching in chromium-doped strontium titanate (Cr:SrTiO₃). Differences in the X-ray absorption near edge spectroscopy (XANES) at the Cr K-edge indicate that the valence of Cr changes from 3+ to 4+ underneath the anode of our sample device after the application of an electric field. Spatially resolved X-ray fluorescence microscopy (μ-XRF) maps show that the Cr⁴⁺ region retracts from the anode-Cr:SrTiO₃ interface after a conducting state has been achieved. This interface region is studied with extended X-ray absorption fine structure (EXAFS) and the results are compared with structural parameters obtained from density functional theory (DFT) calculations. They confirm that oxygen vacancies which are localized at the octahedron with a Cr at its center are introduced at the interface. It is proposed that the switching state is not due to a valence change of chromium but caused by changes of oxygen vacancies at the interface. © 2007 Elsevier B.V. All rights reserved.