Abstract: Gd₂O₃:Eu³⁺ luminescent materials with spherical shape and the size of 20nm were synthesized by a sol-lyophilization method. The XRD patterns and FTIR spectra show that the precursor samples are hydroxide crystals, and the calcined samples are cubic Gd₂O₃. The PL spectra show that the calcined samples emit Eu³⁺ character red light, and there is efficient energy transition from Gd³⁺ to Eu³⁺. With the increasing of calcining temperatures, the intensity of emission and excitation increases and the lifetime becomes longer due to the crystal growing better, and the surface defects are decreased, then the quenching center is also decreased.