The fundamental luminescence and chromaticity properties of a class of red-emitting phosphors LiEu (W O4) 2-x (Mo O4) x under near-UV excitation have been investigated. The photoluminescence (PL) and photoluminescence excitation (PLE) spectra reveal that the absorption is mainly attributed to O→Mo (W) charge transfer at 300 nm and the Eu3+ transitions in near-UV and visible regions, and red emissions are assigned to intraconfigurational 4f-4f transitions of Eu3+. Both PL and PLE intensity were found to increase with increasing doped Mo content. The intensity of the D05 → F27 emission of Eu3+ activated at 394 nm was found to reach a maximum when the relative ratio of MoW was 2:0. The CIE chromaticity coordinates were found to be (0.66, 0.33) for LiEu (Mo O4) 2 and it reached the same level as the commodity phosphor Y2 O2 S: Eu3+. A white-light-emitting diode fabricated using the composition-optimized LiEu (Mo O4) 2 and the matching green- and blue-emitting phosphors shows that the quality of red color reproduction based on LiEu (Mo O4) 2 was found to be much higher and improved than that using La2 O2 S: Eu3+.