Solid-phase extraction for cationic elements is a promising approach for water treatment or for analysis applications. However. supports that allow the selective extraction and/or preconcentration of metalloid species are still not widespread. A new chelating sorbent has been prepared by grafting 2,3-diaminonaphtalene (DAN) on Amberlite (R) XAD-4 resin beads via a diazo bridge. The synthesis was first carried out at a molecular level to optimise experimental conditions and to facilitate characterisation of solid sorbent by FTIR. TGA, Py-GC/MS experiments and back titration of amine functions showed that the sorbent was grafted. Se(IV) was retained by grafted Amberlite (R) XAD-4 with a rate of 88% at pH 2 and 80 degrees C. This paper presents a convenient way of grafting DAN on polystyrene-like resins and the first applications of these supports in solid-phase extraction of Se(IV). (C) 2009 Elsevier Ltd. All rights reserved.