This article describes a convenient method for the synthesis of two new polymeric resins via nucleophilic substitution reactions involving 5,11,17,23-tetrakis[(propylthio)methyl]-25,26,27,28-tetrahydroxycalix[4] arene 4, and 5,11,17,23-tetrakis[(methylthio)methyl]-25,26,27,28-tetrahydroxycalix[4] arene 6, as precursors with Merrifield's resin. The extraction studies were made using both liquid-liquid extraction and solid-liquid batchwise sorption procedures. The calix[4]arene based polymeric resins have high extraction ability toward metal cations and Na2Cr2O7 as compared to their monomeric precursors. (C) 2004 Elsevier Ltd. All rights reserved.