AbstractSugar gourd shaped CeF₃:Tb³⁺ has been successfully synthesized by polyol method. The phase, morphology and fluorescent properties of CeF₃:Tb³⁺ were characterized by X‐ray diffraction (XRD), transmission electron microscopy (TEM), infrared spectroscopy (IR) and photoluminescence (PL) spectra, respectively. It can be seen that the volume changes of giethylene glycol (DEG) and H₂O content did not affect the phase structure of CeF₃:Tb³⁺. The emission spectrum of CeF₃:Tb³⁺ shows the characteristic emissions of Tb³⁺ ion, indicating that an energy transfer from Ce³⁺ to Tb³⁺ occurs in CeF₃:Tb³⁺, and the decay time of CeF₃:Tb³⁺ was not affected by the change of DEG content.