X-ray spectromicroscopy has been successfully applied to determine the evolution of the Cr oxidation state in Portland cement during leaching experiments. To our knowledge, this is the first study that demonstrates the possibility to study the chromium oxidoreduction phenomena in cement materials at natural Cr concentration (approximately 60 ppm) and at the micron scale. Line scans of Cr for Cr(VI) doped (2000 ppm) and undoped samples indicate that the altered layer (0-1000 microm from the surface) is characterized by a lower amount of Cr as compared to the core part, whereas an accumulation appears in the intermediate region (1000-1300 microm). This Cr-rich interface could correspond to an accumulation of ettringite (3CaO x Al2O3 x 3CaSO4 x 32H2O) as reported by previous works. This mineral exhibits the property to incorporate Cr(III) and Cr(VI) by replacement of aluminum and sulfate, respectively, in the structure. The most surprising result concerns the evolution of the Cr(VI)/Cr(tot) ratio along the line spectra, which is constant from the altered layer to the core (both for doped and undoped samples). This means thatthe same amounts of Cr(VI) and Cr(tot) are released during leaching. Even for the undoped sample, Cr(VI) was detected in the altered layer at 40 microm from the surface. This result is not in perfect agreement with literature, which usually states that Cr(VI) is mainly leached out. Although this result must be confirmed, it clearly indicates that Cr(VI) may be less mobile than predicted by models. An attempt is made to identify potential Cr(VI) fixation phases.