Using an improved Bridgman method, 0.3 mol%Tm3+/0.6 mol%Tb3+/y mol%Eu3+(y=0, 0.4, 0.6, 0.8) doped Na5Y9F32 single crystals were prepared. The X-ray diffractions, excitation spectra, emission spectra and fluorescence decay curves were used to explore crystal structure and optical performance of the obtained samples. When excited by 362 nm light, the cool white emission was realized from Na5Y9F32 single crystal triply-doped 0.3 mol% Tm3+/0.6 mol% Tb3+/0.8 mol% Eu3+, in which the CIE coordinate was (0.2995, 0.3298) and the correlated color temperature (CCT) was 6586 K. The integrated normalized emission intensity of the tri-doped single crystal at 448 K can keep 62% of that 298 K. The internal quantum yield (QY) was calculated to be ~ 15.16% by integrating spheres. These results suggested that the single crystals tri-doped Tm3+, Tb3+ and Eu3+ions have a promising potential application for white light-emitting diodes (w-LEDs).