Two scheelite-type rare-earth tungstates LiLn(WO4)2 (Ln=Sm, Eu) have been prepared using a high temperature molten salt method and structurally characterized by single crystal X-ray diffraction (SC-XRD) analyses. The structure features a three-dimensional (3D) network that is composed of two-direction packing of isolated WO4 tetrahedra interconnected by Li|Ln atoms. The photoluminescence (PL) properties of LiLn(WO4)2 (Ln=Sm, Eu) show the characteristic spectra of Sm3+ and Eu3+ ions. The emission spectra of the LiSm(WO4)2 consisted of some sharp emission peaks of Sm3+ ions centred at 562nm, 600nm, 645nm, 705nm, in which the strongest one is 645nm due to 4G5/2→6H7/2 transition of Sm3+. For phosphor LiEu(WO4)2, the emission spectra recorded for excitation wavelength at 393 or 464nm exhibit a strong emission peak at 613nm, corresponding to the 5D0→7F2 transition of Eu3+. The commission international Del’Eclairage (CIE) chromaticity coordinates of the phosphors were about (0.5166, 0.4657) for LiSm(WO4)2 and (0.6240, 0.3701) for LiEu(WO4)2.