Abstract: Li_4-3xEu_x(WO₄)₂ microcrystallines were synthesized by hydrothermal method. The crystal structure, surface morphology and room temperature photoluminescence properties of the microcrystallines were investigated by X-ray powder diffraction (XRD), scanning electron micrograph (SEM) and fluorescence analysis (FL), respectively. XRD results confirmed that all the Li_4-3xEu_x(WO₄)₂ microcrystallines all were typical scheelite structure with tetragonal symmetry. SEM measurements showed that the grain size of Li_4-3xEu_x(WO₄)₂ microcrystallines increased with the increasing x, varying in the range of 2.0 μm×0.2 μm~12 μm×1.0 μm. Fluorescence analysis results revealed that these phosphors can be effectively excited by ultraviolet light (395 nm), emitting the maxium line at 614 nm with pure red light. The emission intensity of the two characteristic emission peaks of Eu³⁺ (located at 593 nm and 614 nm) initially increased, and reached the maximum at 1.0. It then decreases with the increasing x.