A new dimorphic copper selenite bromide, Cu5(SeO3)4Br2 was obtained via chemical transport reactions. α-Cu5(SeO3)4Br2, monoclinic (1m) and β-Cu5(SeO3)4Br2, triclinic (1a) polymorphs were produced simultaneously upon reaction of amorphous, partially dehydrated copper selenite and copper bromide. 1m is similar to Cu5(SeO3)4Cl2, whereas 1a is distantly related to Ni5(SeO3)4Br2 and Co5(SeO3)4Br2. Attempts to reproduce synthesis of 1a via exchange reaction between Na2SeO3 and CuBr2 resulted in a new Na2[Cu7O2](SeO3)4Br4 (2). Current study demonstrates for the first time, that both chemical vapor and exchange reactions can be employed in preparation of new selenite halides.