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This chapter presents a summary that discusses the coordination chemistry of homoleptic thioether macrocycles critically, with emphasis on likely future developments and uses. Some unpublished results, mainly crystallographic data from laboratories, are discussed in this chapter. The coordination chemistry of thioether ligands has undergone a renaissance over the past five years. This has been because of the observation that cyclic thioethers can bind to a range of transition metal ions to form stable metal complexes. The properties of the M-S(thioether) bond can now be studied with a variety of metal centers, oxidation states, and coordination geometries. Another impetus for the study of the coordination chemistry of crown thioethers stems from the role of thioether binding in biological systems, such as d-biotin (involving tetrahydrothiophene), and blue copper proteins, such as plastocyanin …