[en] Highlights: • The energy transfer from Ce³⁺ to Tb³⁺ in NaCaGaSi₂O₇ host is the dipole-dipole interaction, and the efficiency is 83.5%. • The energy transfer critical distance was calculated to be 8 Å. • PL thermal quenching properties of phosphors have been investigated in detail. • The emission colour is tuned from deep blue (0.174, 0.048) to green (0.289, 0.439) by increasing the contents of Tb³⁺ions. - Abstract: The NaCaGaSi₂O₇:Ce³⁺,NaCaGaSi₂O₇:Tb³⁺ and NaCaGaSi₂O₇:Ce³⁺/Tb³⁺ phosphors were synthesized under a weak reducing atmosphere by the traditional high temperature solid state reaction method. The synthesized phosphors were characterized by X-ray diffraction (XRD), fluorescent decay times, photoluminescence (PL) emission and excitation spectra including temperature-dependent PL properties. The effects of Ce³⁺ singly doped and Ce³⁺/Tb³⁺ co-doped concentrations on the structure, luminescence properties and energy transfer of NaCaGaSi₂O₇ phosphors were studied in detail. The results indicated that the energy transfers between Ce³⁺ and Tb³⁺ in the host occurred mainly via a dipole-dipole mechanism, and the critical distances of the ion pairs (R_c) were calculated by the quenching concentration method and spectral overlap method. The Ce³⁺ emission intensity and decay lifetimes decrease with the raise of Tb³⁺ concentration in NaCaGaSi₂O₇:Ce³⁺/Tb³⁺ samples. The above results indicate that NaCaGaSi₂O₇:Ce³⁺/Tb³⁺ can be a candidate as a host material for solid-state lighting and display fields.