LaCeF3∶Tb microcrystalline was synthesized by microemulsion method, oleic acid-assisted solvothermal method, ultrasonic-assisted solvothermal method separately. LaCeF3∶Tb microcrystalline synthesized by ultrasonic-assisted solvothermal method is rarely reported. Using X-ray diffraction (XRD), scanning electron microscope (SEM), fluorescence spectroscopy (PL) method such as the crystal phase, morphology and luminescence properties of the samples have been characterized. XRD results show that the crystallization product is good, microcrystalline and standard card PDF# 38-0452 (the six-party LaCeF3) is corresponding, SEM images showing the product has uniform size and morphology, under 250 nm excitation nanoparticles shows strong green light, the main emission peaks respectively belonged to 5D4→7F6(489 nm), 5D4→7F5(545 nm), 5D4→7F4(585 nm)and 5D4→7F3(621 nm) transition of Tb3+. Through LaCeF3 and LaCeF3∶Tb spectral studies prove the existence of the Ce-Tb energy transfer. Calculated the critical doping concentration of Tb in LaCeF3 microcrystalline synthesized by different methods.