Novel single-phased white-light-emitting Ca9LiGd2/3(PO4)(7):xDy(3+) (x = 0.02, 0.05, 0.10, 0.15, 0.20, 0.25, and 0.30) beta-Ca-3(PO4)(2)-type phosphate phosphors were synthesized. The phase structure, luminescence, and thermal stability of the phosphors were characterized by X-ray powder diffraction analysis, photoluminescence excitation and emission spectra, thermal quenching, and decay curves. XRD analysis confirmed the phase formation of Ca9LiGd2/3(PO4)(7):Dy3+ materials. Under the excitation of 352 nm, the emission of the Ca9LiGd2/3(PO4)(7):0.20Dy(3+) sample centered at blue (488 nm) and yellow (580 nm), which corresponded to F-4(9/2)-H-6(15/2) transition and F-4(9/2)-H-6(13/2) transition. The optimum dopant concentration of Dy3+ ions was around 20 mol%, and the critical transfer distance of Dy3+ was calculated as 181 angstrom. The thermal-quenching temperature was above 500 K for Ca9LiGd2/3(PO4)(7):0.20Dy(3+). The developed phosphor has a great potential as a single-component white-light-emitting phosphor for UV-light-emitting diodes.