A yellow bromobismuthate ((2-BrPy)₂H)[BiBr₄] (1, 2-BrPy=2-bromopyridinium) transforms into the unusually deeply colored cherry-red (2-BrPyH)₂[BiBr₅] (2). A combination of structural studies and theoretical calculations confirms that the appearance of short non-covalent BrBr interactions (≈3.3Å) in 2 is responsible for the anion-to-cation charge transfer (LP(Br_ligand)→σ*(Br-C)), yielding dramatic changes in optical behavior. This effect opens the way towards novel halogen bonding-templated halometalate-based hybrid materials with enhanced optical properties.