Ce3+ ions (2 mol%) doped KY3F10 (Ce: KYF) single crystals were successfully grown by the vertical Bridgman method in a vacuum system. Ce3+: KYF single crystal had high crystalline quality and transmittance, and the absorption edge was significantly red shifted compared with undoped KYF. The broad band emission centered at 360 nm (λex = 300 nm) were both observed in them, while a three-fold increased emission intensity was seen when Ce3+ ions were doped. Ce: KYF crystal possessed high UV luminous efficiency due to converting the light of a 265 nm chip to its luminescence effectively. It was a surprise that Ce: KYF crystal exhibited stable zero-thermal quenching property in the UV band which covered a wide temperature range from 298 K to 573 K. The possible mechanism of the luminescent properties and the superior thermal stability of Ce: KYF was discussed. Ce: KYF single crystal will have good application prospect as an excellent UV luminescent material with high thermal stability.