Binding of S2O32-, SeO42-, Pt(CN)42-, Co(CN)63-, Au(S2O3)23- and Fe(CN)64- anions by the protonated (positively charged) forms of tren (tris(2-aminoethyl)amine) and of the tren-derivative (HL) containing a pyrimidine residue was studied by means of potentiometric measurements in 0.1 M NMe4Cl solutions at 298.1±0.1 K. Both ligands form stable complexes with these anions which appear to be mostly stabilized by electrostatic forces. In the case of HL, also anion-π interaction with the pyrimidine residue of the ligand affords a significant contribution to complex stability. Some shape preference for tetrahedral and octahedral anions over square planar ones is observed. A hybrid AC/HL material obtained by adsorption of HL on commercial activated carbon (AC) was used to study the extraction of these anions from water. AC/HL shows enhanced adsorption capacity toward all the anions studied with respect to AC. This behavior is ascribed to the stronger interaction of anions with the HL function of AC/HL than with the Cπ-H3O+ sites of unfunctionalized AC. Of special interest is the enhancement of the adsorption capacities found for Au(S2O3)23- and Pt(CN)42-, two anions of great relevance for the extraction of platinum-group metals (PGM) from ores and from metallic wastes.