A variety of Ce³⁺ and Tb³⁺ doped Ba₃P₄O₁₃ phosphors were synthesized via the solid state reaction method. Their photoluminescence properties, decay lifetime, thermal stability and luminous efficiency were investigated. The possible energy transfer mechanism was proposed based on the experimental results and detailed luminescence spectra and decay curves of the phosphors. The critical distance between Ce³⁺ and Tb³⁺ was calculated by both the spectral overlap method and the concentration quenching method. The energy transfer mechanism from Ce³⁺ to Tb³⁺ is determined to be dipole–quadrupole interaction. Furthermore, Ba₃P₄O₁₃:Ce³⁺,Tb³⁺ exhibits relatively excellent thermal stability and its intensity remains 92.7% of the initial intensity at 150 °C.