A series of LiLa(MoO4)(2):Eu3+@ (NaF)(y) (wt) were prepared with a simple coating method. XRD results confirm that NaF coating will cause the slight expand of the lattice volume for the sample. Strongly enhanced emission effect inducing by NaF coating is observed. The emission spectra (PL) intensity of the optimal sample, LiLa(MoO4)(2):Eu-0.06(3+)@ (NaF)(0.025wt) is as high as 4.8 times of that of LiLa(MoO4)(2):Eu-0.06(3+). Furthermore, dual emission properties inducing by NaF coating are observed. Enhancement emission of Eu3+ is a major effect, and increasing R is a minor effect. The optimal coating content of NaF is 2.5 wt%, which the corresponding chromaticity coordinates excited at 465 nm is x = 0.6650, y = 0.3347, which is nearly as same as the NTSC (National Television Standard Committee) standard values for red (x = 0.67, y = 0.33). So, it is a potential red-emitting phosphor with high R values (R = 5.89) for blue light-based white LED.