A series of Eu³⁺ or Tb³⁺ doped Ba₂Ca(BO₃)₂ phosphors 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→⁷F₅ transition 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)₂ are 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⁺.