Phosphors of CaLa4Si3O13 singly- and co-doped with Ce3+ and Tb3+, which are suitable for application in white LEDs, were successfully produced by using a high temperature solid state reaction method. Their apatite crystalline structure as well as their photoluminescent properties both at room temperature and at higher temperatures (up to 150 °C) were experimentally determined, which also allowed the determination of the energy transfer efficiency and mechanism in the host lattice from the sensitizer Ce3+ ions to the activator Tb3+ ions. The excitation spectra of the doped phosphors exhibited an intense, broad band from 200 to 420 nm, which is a good match for the UV and near-UV chip (350–420 nm). Under excitation with UV light, two distinct luminescence bands were recorded; a blue one centered at 433 nm, which is typical for Ce3+ emission, and a green one, which peaks at 552 nm, originated from 5D4 → 7F5 transition in Tb3+. •Both Ce3+ and Tb3+ ions occupy La3+ sites in CaLa4Si3O13 host.•The emission color shift from blue to green region in Ce3+/Tb3+ co – doped CaLa4Si3O13 phosphors.•The energy transfer efficiency is increase upto 93% with the increasing of Tb3+ concentration.•Energy transfer mechanism illustrate that dipole-dipole energy transfer are dominant from Ce3+ to Tb3+ ion.•The remaining intensity of green emission of Ce3+/Tb3+ co-doped CaLa4Si3O13 phosphors is 70% at 150 °C.