Ce³⁺/Tb³⁺ co-doped BaClF luminescent materials with highly efficient green luminescent properties. The phosphor was synthesized by a co-precipitation hydrothermal method, and the structure and morphology of the phosphor were characterized using X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), and X-ray photoelectron spectroscopy (XPS). The photoluminescence properties of the prepared products were investigated and the energy transfer efficiencies were calculated for BaClF:3.0 mol% Ce³⁺, ymol% Tb³⁺ ( y = 0–0.5). By adjusting the doping concentration of Tb³⁺ ions in BaClF: Ce³⁺, Tb³⁺ phosphors, the luminescent color of the phosphor can be easily changed from blue to green. The Ce³⁺ and Tb³⁺ co-doped BaClF phosphor shows strong PL emission in the green region due to the resonance energy transfer from Ce³⁺ to Tb³⁺. The energy transfer mechanism of Ce³⁺ and Tb³⁺ co-doped BaClF samples was analyzed based on the energy level relationship between Ce³⁺ and Tb³⁺. The energy transfer efficiency from Ce³⁺ to Tb³⁺ was calculated and found to be up to 89.63%. These results suggest that BaClF: Ce³⁺, Tb³⁺ fluorescent material can be a potential green luminescent material for optoelectronic applications.