The structures, electron affinities and bond dissociation energies of BrO4F/BrO4F- species have been investigated with five density functional theory (DFT) methods with DZP++ basis sets. The planar F-Br center dot center dot center dot O-2 center dot center dot center dot O-2 complexes possess (3)A' electronic state for neutral molecule and (4)A' state for the corresponding anion. Three types of the neutral-anion energy separations are the adiabatic electron affinity (EA(ad)), the vertical electron affinity (EA(vert)), and the vertical detachment energy (VDE). The EA(ad) value predicted by B3LYP method is 4.52 eV. The bond dissociation energies D-e (BrO4F -> BrO4-mF + O-m) (m = 1-4) and D-e(-) (BrO4F- -> BrO4-mF- + O-m and BrO4F- -> BrO4-mF + O-m(-)) are predicted. The adiabatic electron affinities (EAad) were predicted to be 4.52 eV for F-Br center dot center dot center dot O-2 center dot center dot center dot O-2 ((3)A'<- (4)A') (B3LYP method).