Organically-modified silica gels bearing mercaptopropyl and ethylenediaminetriacetate groups (SiO2-SH/ED3A) have been used for reduction and subsequent sequestration of Cr(VI) species. The uptake mechanism involves Cr(VI) reduction by thiol groups (SH) and further immobilization of the so-generated Cr(III) species via complexation to the ethylenediaminetriacetate moieties (ED3A). The most appropriate pH range (1-3) for complete Cr(VI) reduction-sorption by SiO2-SH/ED3A originates from the balance between full reduction of Cr(VI) by SH, requiring low pH values, and quantitative complexation of Cr(III) by ED3A, which is favored in less acidic media. Such bi-functional adsorbents are considerably more effective at removal of Cr(VI) than those simply modified with thiol groups alone. The whole reduction-sorption process was characterized by fast kinetics, thus permitting efficient use of the SiO2-SH/ED3A adsorbent in dynamic conditions (column experiments). Monitoring the amount of immobilized chromium species on the solid was achieved using X-ray fluorescence spectroscopy and UV-vis spectroscopy. Studying the influence of ionic strength and presence of heavy metals revealed few interference on Cr(VI) removal.