The novel scheelite structures of Li2Ca(WO4)2 , Li2Ca2(WO4)(SiO4), and LiCa2(WO4)(PO4) fluorescent materials were successfully prepared using a high-temperature solid-phase method. The compounds were characterized by XRD, EDS, and XRF. The test results showed that the substitution of [WO4]2- by [SiO4]4- /[PO4]3- tetrahedron in tungstate had no significant influence on the crystal structure of the Li2Ca(WO4)2. When Dy3+ ions were introduced as an activator at an optimum doping concentration of 0.08% mol, all of the as-prepared phosphors generated yellow light emissions, and the emission peak was located close to 576 nm. Replacing [WO4]2- with [SiO4]4- /[PO4]3- tetrahedron significantly increased the luminescence of the Li2Ca(WO4)2 phosphors. In addition, the LiCa2(WO4)(PO4):zDy3+ phosphors had the best luminescence properties, decay life (τ = 0.049 ms), and thermal stability (87.8%).