A mesoporous silica (SBA-15) and amorphous silica (SG) have been chemically modified with 2-mercaptopyridine using the homogeneous route. This synthetic route involved the reaction of 2-mercaptopyridine with 3-chloropropyltriethoxysilane prior to immobilization on the support. The resulting material has been characterized by powder X-ray diffraction, nitrogen gas sorption, FT-IR and MAS NMR spectroscopy, thermogravimetry and elemental analysis. The solid was employed as a Cr(VI) adsorbent from aqueous and non-aqueous solutions at room temperature. The effect of several variables (stirring time, pH, metal concentration and OF solvent polarity) has been studied using the batch technique. The results indicate that under the optimum conditions, the maximum adsorption value for Cr(VI) was 1.83 +/- 0.03 mmol/g for MP-SBA-15, whereas the adsorption capacity of the MP-SG was 0.86 +/- 0.02 mmol/g. On the basis of these results, it can be concluded that it is possible to modify chemically SBA-15 and SG with 2-mercaptopyridine and to use the resulting modified silicas as effective adsorbents for Cr(VI). (c) 2006 Elsevier Ltd. All rights reserved.