In this paper, the adsorption selectivity and mechanism of diethylenetriamine (DETA)-functionalized PGMA adsorbent (denoted as P-DETA) toward a number of heavy metal ions, including Cu, Co, Ni, Zn, and Cd ions, were experimentally and analytically examined. Experimental results showed a selective adsorption sequence, based on the adsorption affinity, of Cu > Co > Ni > Zn > Cd ions on P-DETA. X-ray absorption fine structure (XAFS) analysis was used to reveal the adsorption coordination geometry, bond length, and coordination number of each type of metal ion with the DETA group. The analysis indicated that Cu, Ni, and Zn ions formed tetrahedral geometry (fourfold coordination) when adsorbed, while Co ion showed an octahedral geometry (sixfold coordination). However, the coordination geometry for Cd could not be obtained in the analysis due to the lack of reference information. The analysis from EXAFS further confirmed that the ratio of DETA ligand to the adsorbed metal ion was probably 1 for Cu, Ni, or Zn ions, while that ratio was 2 for Co ion. From the stability constant (in the log K form) for a metal ion-DETA ligand coordination (denoted as MLn, where M indicates a heavy metal ion, and L-n indicates n numbers of ligands involved), a relationship of log K (CuL) > log K (CoL2)> log K (NiL) > log K (ZnL) > log K (CdL) is suggested. This sequence is in good correlation with the experimentally derived adsorption selective sequence of Cu > Co > Ni > Zn > Cd ions, indicating that the coordination geometry played an important role in the determination of the adsorption selectivity for heavy metal ions by the polyamine-functionalized adsorbent of P-DETA. (C) 2010 Elsevier Inc. All rights reserved.