The extraction properties of dibenzo-1, 10-dithia-[18]crown-6 compounds have been investigated. Especially thiophilic metals are effectively extracted. The extraction of Ag(I), Pd(II) and Au(III) is much greater than that of Hg(II) or Cu(I). Alkali and alkaline earth metals are not extracted. The experimental results show the coordination of metal ions with sulfur is decisive for the extraction. The variation of the subetituents at the macrocyclic ring from CH3- t o CH2Cl-groups influences the extraction power considerably. In contrast, the substitution on the benzo groups shows a less strong effect. The influence of diluents and counter anions on extraction are comparable with results in known crown ether systems. Synergistic extraction is observed for silver and mixtures of dithiacrown compounds and HDEHP, n-caprylic acid or TBP.