Threshold collision-induced dissociation of M+(C6H5F) and M+(C6H5F)(2) with Xe is studied by guided ion beam mass spectrometry. M+ include the following alkali metal ions: Li+, Na+, K+, Rb+, and Cs+. In all cases. the primary and lowest energy dissociation channel observed is endothermic loss of an intact fluorobenzene ligand. Sequential dissociation of a second fluorobenzene ligand is observed at elevated energies in the bis complexes. Minor production of ligand exchange products. M+Xe and M+(C6H5F)Xe, is also observed. The cross section thresholds for the primary dissociation channel are interpreted to yield 0 and 298 K bond dissociation energies for (C6H5F)(x-1)M+-C6H5F, x = 1 and 2, after accounting for the effects of multiple ion-neutral collisions, the kinetic and internal energies of the reactants, and dissociation lifetimes. Density functional theory calculations at the B3LYP/6-31G* level of theory are used to determine the structures of these complexes and provide molecular constants necessary for the thermodynamic analysis of the experimental data. Theoretical binding energies are determined from single-point energy calculations at the MP2(full)/6-311 +G(2d,2p) level using the B3LYP/6-31G* geometries. Zero-point energy and basis-set superposition error corrections are also included. The agreement between theory and experiment is very good when full electron correlation is included (for Li-, Na+, and K+), except for the Li+(C6H5F) complex, and reasonable when effective core potentials are used (for Rb- and Cs+). The trends in M+(C6H5F) binding energies are explained in terms of varying magnitudes of electrostatic interactions and ligand-ligand repulsion in the complexes. Comparisons are also made to previous theoretical and experimental BDEs of M+(C6H6), and M+(C6H5CH3)(x), to examine the influence of the fluoro substituent on the binding and the factors that control the strength of cation-pi interactions.