Large-scale CaF 2 -YF 3 alkaline-earth ternary fluoride microspheres with diameters of about 2.5 mm were prepared by a facile hydrothermal method in the presence of disodium ethylenediamine tetraacetate (Na 2 H 2 L). The influences of several experimental parameters, such as reaction time, amount of Na 2 H 2 L, pH values, and fluoride source on the final products were investigated. The formation mechanism of the as-obtained microspheres was proposed on the basis of all these studies. It is also found that the addition amount of the Y 3+ ions had an effect on the morphology of CaF 2 -YF 3 . The luminescence spectrum of Eu 3+ -doped CaF 2 -YF 3 microspheres showed the strong characteristic dominant emission of the Eu 3+ ions at 590 nm, indicating that the Eu 3+ ions occupy a site of inversion symmetry in the CaF 2 -YF 3 matrix.