Rhodium(III) and ruthenium(III) were extracted from chloride solutions with phosphonium ionic liquids trihexyl(tetradecyl)phosphonium chloride or trihexyl(tetradecyl)phosphonium bis(2,4,4-trimethylpentyl)phosphinate in toluene. Influence of HCl and NaCl presence in the feed and IL concentration in the organic phase were determined. Rh(III) transport appeared to be inefficient, while over 70% of Ru(III) was extracted from 3 M HCl. Ru(III) extraction was affected by the feed acidity and the type of extractant used. The spectra of the extracts indicated some changes in the structure of Rh(III) and Ru(III) complexes in the organic phase. Also, ageing of feed solutions on the extraction of Ru(III) and Rh(III) was studied.