The extraction of palladium (II) from chloride solutions (over a wide region of aqueous acidity) by di(2-ethylhexyl)dithiophosphates of tetraoctylammonium, tri-n-octylammonium and di-n-octylammonium in toluene at the constant chloride concentration has been studied. A synergistic effect was shown to be observed in these systems and it is explained by the formation of unusual complexes with mixed ligands. It has been established the palladium complexes, such as (R3NH)[PdCl2A], (R3NH)[PdCl2A] and (R2NH2)[PdCl2A], involving both alkylammonium cation and dialkyldithiophosphate anion are extracted under conditions of the loaded organic phase using distribution methods depending on a composition of aqueous and organic phase. At the excess of R3NHA or R2NH·HA, PdA2is extracted into the organic phase. Table 8 reports the results obtained and indicates the domains of existence of the various species of palladium (II) extracted into the organic phase in the binary ex-tractant systems in comparison with the initial systems