Three novel polybromide complexes of bismuth(III) – (2,6-MePyH)3[BiBr5(Br3)] (1), (H2bpp){[BiBr5](Br2)} (2) and (3-ClPyH)2{[BiBr5](Br2)} (3) – were synthesized. The results of an extended screening involving a set of organic cations resulting in the formation/non-formation of Bi(III) polybromides are presented and discussed. The nature of Br⋯Br interactions in Bi(III) polybromides was investigated by theoretical methods, enabling the estimation of their energies.