[Tris(2-pyridylthio)methyl] zinc fluoride, [kappa(4)-Tptm]ZnF, the first example of an organozinc compound that features a terminal fluoride ligand, may be obtained by the reactions of either [Tptm]ZnX (X = H, OSiMe3) with Me3SnF or [kappa(4)-Tptm]ZnI with [(Bu4N)-N-n]F. Not only is the fluoride ligand of [kappa(4)-Tptm]ZnF susceptible to coordination by B(C6F5)(3) to give the adduct [kappa(4)-Tptm]ZnFB(C6F5)(3), but it is also an effective hydrogen bond and halogen bond acceptor. For example, X-ray diffraction studies demonstrate that [kappa(4)-Tptm]ZnF forms an adduct with water in which hydrogen bonding between the fluoride ligands and water molecules serves to link pairs of [kappa(4)-Tptm]ZnF molecules with a [F center dot center dot center dot(H-O-H)(2)center dot center dot center dot F] motif. Furthermore, H-1 and F-19 NMR spectroscopic studies provide evidence for hydrogen bonding and halogen bonding interactions with indole and C6F5I, respectively.