New solid-phases for the binding, separation and extraction of perrhenate and pertechnetate (ReO(4)(-) and TcO(4)(-)) from water solutions have been developed from a selective molecular receptor. Host compounds being capable of encapsulating these oxoanions are of great interest. The azacryptand, containing two tripodal tetra-amine subunits covalently linked by p-xylyl spacers, is known to display high affinity for ReO(4)(-) and TcO(4)(-) in water. The syntheses of new solid phases, obtained by fixing the receptor on mesoporous silica MCM-41 and Amberlite CG50 supports, are here described. FT-IR, micro-Raman, elemental analysis (CHN), sorption isotherms, (29)Si MAS NMR, and SEM/EDS were employed for solids characterisation. Promising performances were found for silica derivatives, for which the amount of the receptor fixed on silica ranged from 0.2 to 0.3 mmol g(-1). The perrhenate sorption mechanism was investigated with the aim to select the conditions for application in batch and fixed bed column systems.