Eu 2+ activated Ca 5(PO 4) 3Cl blue-emitting phosphors were prepared by the conventional solid state method using CaCl 2 as the chlorine source and H 3BO 3 as flux. The structure and luminescent properties of phosphors depend on the concentrations of Eu 2+, the amount of CaCl 2 and the usage of the H 3BO 3 flux were investigated systematically. Eu 2+ and Mn 2+ Co-doped Ca 5(PO 4) 3Cl with blue and orange double-band emissions were also researched based on the optimal composition and synthesis conditions. The energy transfer between Eu 2+ and Mn 2+ was found in the phosphor Ca 5(PO 4) 3Cl:Eu 2+, Mn 2+, and the Co-doped phosphor can be efficiently excited by near-UV light, indicating that the phoshor is a potentional candidate for n-UV LED used phosphor.