Mononuclear polyoxathia[n]ferrocenophanes (8a–d) and binuclear polyoxadithia[n,n]ferrocenophanes were synthesized by the reaction of 1,1′-bis(ω-chloropolyethyleneoxy)ferrocene with sodium sulfide in N,N-dimethylformamide and the complexing ability of 8a–d with alkali and transition metal cations was measured by an extraction method. Compound 8d extracts a thallium ion specifically, the extraction efficiency of several ions being in the order: Tl+>>Rb+>K+>Cs+>Na+>Li+.