Our study focused on the leaching processes in soil contaminated with hexavalent chromium (Cr(VI)), traced to industrial waste from a disused site and resulting in groundwater contamination. Mineral and geochemical characterization of the soil by means of XRD, SEM-EDS, total digestion and sequential extractions revealed that the main Cr content was from solid waste located in the upper meter of the soil profile. Flow-through and column experiments were carried out to investigate the processes responsible for Cr(VI) release. Cr(VI) mobility along the soil profile was also assessed. Moreover, Cr isotope signatures were used to evaluate a potential Cr(VI) reduction process, which preferably could immobilize toxic Cr(VI) complexes. One-dimensional (1D) numerical simulations reproduced the Cr(VI) release from the flow-through experiment containing the Cr(VI) rich-solid waste and also the Cr(VI) mobility along the column experiment. These results enabled us to interpret quantitatively the processes resulting in Cr(VI) contamination and mobility along the soil profile. Cr(VI) was released from dissolving Cr(VI)-rich phases (e.g., sodium chromate, Cr(VI)-hydrocalumite and Cr(VI)-ettringite) of the solid waste layer. Cr(VI) reduction and Cr(VI) adsorption did not take place along the column. Such accurate characterization of these processes is necessary for the mitigation of Cr(VI) mobility in contaminated soils.