The molecular structures, electron affinities, and dissociation energies of the BrFn/BrFn- (n = 1-7) molecules have been examined using hybrid Hartree-Fock/density functional theory (DFT). The three different types of electron affinities reported in this work are the adiabatic electron affinity (EA(ad)), the vertical electron affinity (EA,,), and the vertical detachment energy (VDE). The first Br-F dissociation energies of the BrFn and BrFn- species have also been reported. The basis set used in this work is of double-zeta plus polarization quality with additional s- and p-type diffuse functions, and is denoted as DZP(++). Four different density functionals were used in this work. Among these, the best for predicting molecular structures and energies was found to be BHLYP, while other methods generally overestimated bond lengths. The most reliable adiabatic electron affinities, obtained at the DZP++ BHLYP level of theory, are 3.41 (Br), 2.64 (BrF), 4.78 (BrF2), 3.77 (BrF3), 5.58 (BrF4), 4.24 (BrF5), and 5.59 eV (BrF6). The electron affinity of the Br atom predicted by this work is in good agreement with the experimental result, but not one of the molecular electron affinities (BrF,, 1-7) is known. The neutral BrFn bond distances range from 1.70 to 1.83 Angstrom. However, the diatomic BrF- distance and the axial Br-F distances in BrF3-and BrF5-:;are much longer, 2.25-2.30 Angstrom, suggesting that the bonding in these three anions is quite different from that of their neutral counterparts.