The bromide complexes of copper(II) were studied spectrophotometrically in acetic acid. This non-dissociating solvent presents secondary equilibria such as perchlorate ⇌ acetate and in the case of copper acetate in acetic acid, monomer ⇌ dimer. A matrix rank treatment of the optical densities identified four mononuclear bromo complexes which are formulated as Cu(OAc)Br, CuBr2, LiCuBr3 and Li2 CuBr4. The overall stability constants of these species are log β1 = 3.2, log β2 = 6.5, log β3 = 7.7 and log β4 = 7.7. The electronic spectra of the individual species, in this solvent, are reported for the first time. The d-d transition band of the tetrabromocuprate is calculated to be at 1120 nm and confirms the structure of a flattened tetrahedron.