The Gd₂O₃: Eu³⁺ phosphor co-doped with Li⁺ and Na⁺ were prepared by precipitation method and compared with the samples prepared by microwave solid state phase method. The X ray diffraction, the excitation spectra and the emission spectra of the samples were measured. The microstructure of the samples was analyzed, and the effect of different synthesis conditions on the photoluminescence properties of Gd₂O₃: Eu³⁺ phosphor was discussed. The results showed that without adding Li+ ions, the luminous intensity of the sample obtained by precipition increased about 1.68 times compared with the sample prepared by the microwave solid phase method. Adding Li⁺ ions, the luminous intensity of the sample obtained by precipition increased 1.82 times compared with it obtained by the microwave solid phase method. The emission of the sample with 4.5 mol% Li⁺,4.5 mol% Na⁺  and 4.5 mol% Eu3⁺  co-doped Gd₂O₃ increased 5.91 times than that of the sample without adding Li⁺ and Na⁺ ions by C₂H₂O₄ precipitation.