Copper halide based organic-inorganic hybrid semiconductors exhibit great potentials as light-emitting materials with excellent structural variety and optical tunability. Among them, copper halide hybrid molecular compounds with discrete inorganic modules are particularly interesting due to their high quantum efficiency, however, synthesizing highly efficient blue-emitting molecular clusters remains challenging. Here, we report a novel and facile strategy for the design and synthesis of highly luminescent copper halide hybrid structures by fabricating coordinated anionic inorganic modules in these ionic species. Under such approach, a family of strongly blue-emitting copper halide hybrid ionic structures are prepared with high internal quantum yields up to 98%. Strong luminescence from the combination of ionic and covalent bonds in these compounds make them ideal candidates as alternative, rare-earth element free light-emitting materials for possible use in optoelectronic devices.