Highly luminous hollow chloroapatite blue phosphors were directly synthesized by an aerosol route. It is noteworthy that the hollow structures of the chloroapatite phosphors were achieved in a rapid manner (within several seconds) without using any templates, which offers tremendous advantages, such as saving time and energy, freedom from contamination, a lowering density, and a reduction of costs for both templates and raw materials. The as-prepared phosphors exhibited extremely high quantum efficiency (QE, as high as 100% under 365 nm excitation), showing great promise for white light-emitting diode (LED) application.