New lariat ethers, N-(o-fluorophenyl)aza-15-crown-5 (F-A15C5) and N,N′-bis(o-fluorophenyl)diaza-18-crown-6 (F₂-A₂18C6), were prepared by the N-arylation of the corresponding azacrown ethers. The interaction of the ligands with metal cations was studied in solution by ¹H and ¹⁹F NMR (in acetone-d₆) and UV spectroscopy (MeOH) confirming the formation of complexes of F₂-A₂18C6 with K⁺, Na⁺, Ag⁺, Ba²⁺, Pb²⁺ and of F-A15C5 with Na⁺ and giving evidence of CF⋯metal cation interaction. Cation binding constants (β, evaluated by UV titration method), demonstrate that F-A15C5 and F₂-A₂18C6 form more stable complexes than their fluorine-free analogs. The effect depends on the nature of the metal cation and is at a maximum for hard, singly charged cations (up to 3 logβ units for K⁺ complex of F₂-A₂18C6). The X-ray structures of complexes [Pb(F₂-A₂18C6)(H₂O)](ClO₄)₂ (1) and [Ba(F₂-A₂18C6)(ClO₄)₂] (2) reveal short Pb–F (2.805 Å) and Ba–F (2.965 Å) contacts. Complex 2 is centrosymmetric (C_i), while complex 1 has C₂ symmetry with one-side coordination of o-fluorophenyl groups to Pb²⁺. This “one-side” coordination mode of Pb²⁺ is indicative of a partial localization of the Pb²⁺ lone pair.