A series of Eu3+/Tb3+/Mn2+-ion-doped Ca19Ce(PO4)(14) (CCPO) phosphors have been prepared via the conventional high-temperature solid-state reaction process. Under UV radiation, the CCPO host presents a broad blue emission band from Ce3+ ions, which are generated during the preparation process because of the formation of deficiency. The Eu3+-doped CCPO phosphors can exhibit magenta, to red-orange emission as a result of the abnormal coexistence of Ce3+/Ce4+/Eu3+ and the metal metal charge-transfer (MNCT) effect between Ce3+ and Eu3+. When Tb-3/Mn2+ ate doped into the hosts, the samples excited with 300 nm UV light present multicolor emissions due to energy transfer (ET) from the host (Ce3+) to the activators with increasing activator concentrations. The emitting colors of CCPO:Tb3+ phosphors can be tuned from blue to green, and the,CCPO:Mn2+ phosphors can emit red light. The ET mechanism from the host (Ce3+) to Tb3+/Mn2+ is demonstrated to be a dipole-quadrapole interaction for Ce3+ -> Tb3+ and an exchange interaction for Ce3+ -> Mn2+ CCPO:Tb3/Mn2+. Abundant emission colors containing white emission were obtained in the Tb3+ - and Mn2+-codoped CCPO phosphors through control of the levels of doped Tb3+ and Mn2+ ions. The white-emitted CCPO:Tb3+/Mn2+ phosphor exhibited excellent thermal stability. The photoluminescence properties have shown that these materials might have potential for UV pumped white-light-emitting diodes.