Our recent work with cyclic and acyclic polyether self-assembled monolayers (SAMs) on gold is presented. A series of dithia-crown-tetrathiafulvalene derivatives with one or two disulfide groups has been prepared, and their SAMs on gold have been characterized by electrochemistry and by reflection–absorption infrared spectroscopy. These SAMs are extremely stable on repeated electrochemical potential scans and can selectively recognize alkali metal ions. Acyclic polyether derivatives can also self-assemble on gold to yield selective metal ion recognition domains. Impedance spectroscopy data for these SAMs fit the Langmuir isotherm and allow the determination of ion association constants. Some of the SAMs prepared with new acyclic polyether derivatives are able to detect potassium cations selectively when templated in their presence. These structures are believed to be a consequence of ion “imprinting” during the process of SAM formation.