The Ba5SiO4Cl6:Bi3+ phosphor was synthesized by high-temperature solid-state reaction and its luminescence property was investigated. The results showed that the Bi3+-doped Ba5SiO4Cl6 phosphors exhibited an intense blue-white light emission located at 480 nm and a broad excitation band from 230 to 340 nm. The Bi3+-doped Ba5SiO4Cl6 phosphors can be efficiently excited by the incident light of 220-340 nm, and the emission properties of the Bi3+-doped Ba5SiO4Cl6 samples are strongly dependent on the excitation wavelength. The emission color tunability can be obtained by changing the excitation wavelength. The visible region emission characteristics of Ba5SiO4Cl6:Bi3+ indicates that it can potentially be used as a new efficient blue-white luminescent material.