Dark green cuboid-shaped crystals of the composition {[P(o-tolyl)(3)]Br}(2)[Cu2Br6](Br-2) are obtained by the reaction of P(o-tolyl)(3) and CuBr2 with Br-2 in the ionic liquid [NMeBu3][N(Tf)(2)]. The bromocuprate crystallizes triclinic [space group Pi; Z = 1; a = 10.667(2) angstrom; b = 10.695(2) angstrom; c = 11.582(2) angstrom; alpha = 74.42(3)degrees; beta = 75.64(3)degrees; and gamma = 85.68(3)degrees]. The title compound is constituted of ([P(o-tolyl)(3)]Br}(+) cations and [Cu2Br6](2-) anions and contains molecular dibromine [d(Br-Br), = 2.341(1) angstrom]. The latter is verified by thermogravimetry and mass spectrometry.