Abstract Distribution ratios of palladium(II) between hydrochloric acid solutions and some non-polar sorbents in the presence of various reagents containing amino groups were determined. The sorption of palladium is caused by the formation of hydrophobic ionic associates of PdCl 4 2− anion with protonated amines. The recovery of palladium depends on the hydrophobic properties of ion associates and on the sorption behaviour of the amines themselves. The system involving hyper cross-linked polystyrene SSPS and 4- n-octyldiethylenetriamine was chosen for the on-line preconcentration of palladium. Conditions for the quantitative recovery and desorption of the metal were found. A FIA–FAAS method for the determination of palladium including on-line sorption preconcentration has been developed.