Phytomanagement could be a viable alternative in areas polluted with wastes from chromium-using industries. This study investigated the ability of Silene vulgaris to take up Cr(III) and Cr(VI) with special attention on the mechanism used by this species to tolerate high doses of Cr(VI). Plants were grown semihydroponically with different concentrations of either Cr(III) or Cr(VI). A combination of synchrotron X-ray spectroscopic techniques, scanning electron and light microscopy and infrared spectroscopy were used to determine the distribution and speciation of Cr. S. vulgaris accumulated more Cr when grown with Cr(VI) resulting in an overall reduction in biomass. Starch accumulation in leaves may be attributed to an impartment between carbon utilization and assimilation resulted from stunted plant growth but not the complete inhibition of photosynthesis indicating that S. vulgaris possess tolerance mechanisms that allows it to survive in Cr(VI) rich environments. These primary tolerance mechanisms are (a) the total reduction of Cr(VI) to Cr(III) in the rhizosphere or just after uptake in the fine lateral root tips and (b) chelation of Cr(III) to the cell wall both of which reduce metal interference with critical cell functions. These mechanisms make S. vulgaris suitable for in situ remediation of Cr polluted soils.