A series of structurally novel anion receptors 3, 4, and 5 in which a ferrocene unit and a fluorescent moiety are linked to two imidazolium rings have been designed and prepared from 1,1′-bis(imidazolylmethyl)ferrocene. Their crystal structures revealed that these receptors are capable of incorporating anions such as PF₆⁻ and Br⁻. Consequently, the anion binding studies were carried out using various techniques including electrochemistry (CV and OSWV), fluorescence, UV-vis, and ¹H NMR spectroscopy. All the receptors showed a special electrochemical response to the F⁻ anion with a remarkable cathodic shift of more than 260 mV and displayed a unique selectivity for F⁻ and AcO⁻ anions with fluorescence enhancement over various other anions of present interest (Cl⁻, Br⁻, I⁻, HSO₄⁻, H₂PO₄⁻). In addition, for receptor 5, obvious absorption changes were observed when the H₂PO₄⁻ anion was added while other anions (F⁻, Cl⁻, Br⁻, I⁻, AcO⁻, HSO₄⁻) showed only a minor influence on the UV-vis spectra. ¹H NMR titrations demonstrated that receptors 3 and 4 can bind anions through (C–H)⁺⋯X⁻hydrogen bonds and showed strong affinity and high selectivity for the AcO⁻ anion in acetonitrile.