[en] Ion-chromatography (IC) as well as high performance liquid chromatography (HPLC) techniques have been used as analytical tools for the separation and estimation of some of the relevant metal ions present in the high level liquid waste (HLLW). IC was applied for the estimation of alkali and alkali earth metal ions, viz. Na, Cs, Ba and Sr using methane sulphonic acid as the eluent on a cation exchange column. On the other hand, dynamically modified (with sodium salt of n-octane sulphonic acid) reverse phase HPLC was followed for the estimation of lanthanides viz. La, Pr, Nd and Sm using α-hydroxy isobutyric acid as the eluent on a C-18 column. Sample acidity of 0.01 M HNO₃ was optimized for best analytical results. The interferences of one group of metal ions on the quantification of the other group of metal ions were studied. The solvent extraction data (distribution coefficient data) of Na, Cs, Sr, Ba, La, Pr, Nd and Sm from their mixture was obtained by analyses of the aqueous samples before and after extraction with extractants used for actinide partitioning, viz., octyl(phenyl)N,N-diisobutyl carbamoyl methylene phosphine oxide (CMPO), N,N'-dimethyl-N,N'-dibutyl tetradecyl malonamide (DMDBTDMA) and N,N,N',N'-tetraoctyl diglycolamide (TODGA). The solvent extraction data obtained by IC/HPLC techniques was compared with those obtained by ICP-AES technique. A good agreement between the results of the two techniques validated the present analytical method. (author)