8-Hydroxyquinoline and imidazole, two important N-heteroaromatic systems, have a strong affinity towards various anions via their acidic OH or NH protons. Three receptor ligands, 5-(1H-benzo[d]imidazol-2-yl)quinolin-8-ol (1), 5-(benzo[d]thiazol-2-yl)quinolin-8-ol (2), and 4-(1H-benzo[d]imidazol-2-yl)benzene-1,3-diol (3), were synthesized, and their fluoride (F-) ion binding properties were investigated. These ligands could selectively bind F- ions, and their respective F- complexes, namely, 1-TBAF, 2-TBAF, and 3-TBAF (TBAF = tetrabutylammonium fluoride), were characterized using single crystal X-ray analysis, NMR, UV-vis, Hirshfeld surface (HS) analysis and computational studies. Their solid-state structural analysis revealed that in each case, the F- ion is strongly bound within the receptor molecule scaffold through NH, OH, and aryl-CH hydrogen bonding interactions. In the case of 1-TBAF and 3-TBAF, F- binding is further strengthened by the inclusion of water molecules, forming fluoride-water cluster complexes. 1H NMR study exhibited the disappearance of NH and OH proton signals upon the addition of TBAF, indicating that the NH and OH protons are the primary sites for F- ion coordination. UV -vis absorbance spectra was used to study their lowest sensing limits towards F- ions. Ligands 1 and 2 showed good responsiveness towards F- ions at concentrations ≥0.5 μM, with obvious changes occurring at F- concentrations of 180 and 12 μM, respectively. HS analysis quantified non-covalent interatomic contacts between the atoms and fluoride ions, revealing that 1-TBAF contributed a maximum of 19.2% of all atoms⋯F contacts to the HS. Density functional theory studies were carried out on the 1-TBAF, 2-TBAF, and 3-TBAF crystal systems, and the band structure and total density of states of the systems were evaluated. The optical response of 2-TBAF was also investigated.