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