The synthesis of several ferrocene crown ethers is described, which were designed tb selectively coordinate and recognize electrochemically small group I ions sandwiched between two 12-membered crown ether rings. The reactions of the [1,1’-ferrocenediylbis(methylene)]bis[pyridinium] salt [Fcdiyl(py)(2)(2+)] with diaza-12-crown-4 [H(N-2-12-C-4)H], aza-12-crown-4 [H(N-12-C-4)], and 1,2-ethanediylbis(1,7-dioxa-4,10-diazacyclododecane) [C(2)H(4)diyl-((N-2-12-C-4)H)(2)] yielded the respective ferrocene crown ethers 1,1 ":1’,1"’-bis(ferrocenediyl)bis[4,10-bis(methylene)-1,7-dioxa-4,10-diazacyclododecane)] 10-diazacyclododecane)] Fcdiyl(N-2-12-C-4)(2)Fcdiyl] (3), [Fcdiyl(N-12-C-4)(2)] (2), and [Fcdiyl(N-2-12-C-4)(2)(C(2)H(4)diyl)] (4). Complexation of group 1 ions was evidenced by NMR, cyclic voltammetry, FAB mass spectrometry, and picrate extraction experiments. This last techniques was used to determine a complexation selectivity of 4 for Li+/Na+ approximate to 20:1. The redox potentials of the ligands 2, 3, and 4 were determined by cyclic voltammetry; addition of Li+ or Na+ results in anodic shifts of the redox potentials of up to 100 mV for (4Na+ and 140 mV for(4Li+. The X-ray crystal structures of [(2)NaClO4](2), [(2)NaBPh(4)](2), 3, 3 . 2HClO(4), 4, and (4)NaI were determined to understand the coordination behavior of these ligands and the metal ion selectivities displayed.