The preparation of red phosphor in the phosphor-converted white LED is indispensable, and plays a very important role in improving the color rendering index. As a newly developed kind of red phosphor, LiEuW2O8 shows great potential. The luminescence properties of LiEuW2O8 phosphor doped with rare-earth ions are studied. LiEu1-xRExW2O8 (RE=La and Sm) series red phosphors are produced by the high-temperature solid-phase synthesis method. When La3+ and Sm3+ replace Eu3+ in LiEuW2O8, both of them transfer energy to Eu3+ through reabsorption and thus realizing sensibilization of Eu3+. After being doped with La3+ and Sm3+, the excitation and emission peaks of LiEuW2O8 and the crystal structure do not change; however, the luminescence intensity is improved. With the addition of La3+ and Sm3+ of 3% and 4% (molar fraction), respectively, the luminescence intensity reaches the maximum.