A new chromatographic extraction method has been developed using Amberlite XAD-16 (AXAD-16) resin chemically modified with (3-hydroxyphosphinoyl-2-oxo- propyl)phosphonic acid dibenzyl ester (POPDE). The chemically modified polymer was characterized by 13C CPMAS and 31P solid-state NMR, Fourier Transform-NIR-FIR-Raman spectroscopy, CHNPS elemental analysis, and thermogravimetric analysis. Extraction studies performed for U(VI), Th(IV), and La(III) showed good distribution ratio (D) values of approximately 10 3, even under high acidities (1-4 M). Various physiochemical parameters that influence the quantitative metal ion extraction were optimized by static and dynamic methods. Data obtained from kinetic studies revealed that a time duration of ≤ 10 min was sufficient to achieve complete metal ion extraction. Maximum metal sorption capacity values under optimum pH conditions were found to be 1.38, 1.33, and 0.75 mmol g-1 for U(VI), Th(IV), and La(III), respectively. Interference studies performed in the presence of concentrated diverse ions and electrolyte species showed quantitative analyte recovery with lower limits of analyte detection being 10 and 20 ng cm -3 for U(VI) and both Th(IV) and La(III), respectively. Sample breakthrough studies performed on the extraction column showed an enrichment factor value of 330 for U(VI) and 270 for Th(IV) and La(III), respectively. Analyte desorption was effective using 15 cm3 of 1 M (NH 4)2CO3 with >99.8% analyte recovery. The analytical applicability of the developed resin was tested with synthetic mixtures mimicking nuclear spent fuels, seawater compositions and real water and geological samples. The rsd values of the data obtained were within 5.2%, thereby reflecting the reliability of the developed method. © Springer-Verlag 2004.