Contrary to expectations, molecular bromine addition to trans-Pt(Br)(9-anthracenyl)(PEt3)(2) does not result in Pt oxidation or Pt-C bond cleavage but rather in selective multiple bromination of the anthracenyl ligand. The resulting complexes are highly photoluminescent in the blue region due to triplet-triplet annihilation induced delayed fluorescence from the anthracene.