A series of Tb3+ and Eu3+ singly doped and codoped apatite-type Ca4La6(SiO4)(4)(PO4)(2)O-2 phosphors have been prepared by the high temperature solid-state reaction method, and their photoluminescence properties and energy transfer behaviors were investigated in detail. Under excitation by UV light at 376 nm, tunable emission from green to red light is generated due to the Tb3+ transition of D-5(4)-(7)FJ and the Eu3+ transition of D-5(0)-(7)FJ, and emission evolution from green (0.2723, 0.3857) to orange (0.3527, 0.2876) is achieved by adjusting the concentration ratio of the Tb3+-Eu3+ ions. In addition, the energy transfer process between Tb3+ and Eu3+ ions was investigated and demonstrated to be a resonant type via a quadrupole-quadrupole mechanism. This study indicated the potential of Ca4La6(SiO4)(4)(PO4)(2)O-2:Tb3+, Eu3+ phosphors as candidates for color converters in phosphor-converted white light-emitting diodes.