A series of Eu³⁺or Tb³⁺doped Ba₂Ca(BO₃)₂phosphors were synthesized by a high temperature solid state method, and the luminescence properties are investigated. Ba₂Ca(BO₃)₂:Tb³⁺can show an obvious green emission, and the peak locates at 551 nm, which corresponds to the ⁵D₄→⁷F₅transition of Tb³⁺. Ba₂Ca(BO₃)₂:Eu³⁺can present the characteristic emission of Eu³⁺, and the peak locates at 600 nm, which is ascribed to the 5D0→7F2 transition of Eu3+. In order to achieve the emission-tunable phosphors, the Eu³⁺/Tb³⁺co-doped Ba₂Ca(BO₃)₂are synthesized. When tuning the Eu³⁺or Tb³⁺concentration, Ba₂Ca(BO₃)₂:Eu³⁺, Tb³⁺can both show the tunable emission, which may be induced by the energy transfer from Tb³⁺to Eu³⁺.