In this article, Eu-activated CaF2 single crystals were synthesized by Bridgman-Stockbarge method. The dependence of photoluminescence properties of Eu: CaF2 crystals in UV-Vis regions on EuF3 doping concentrations were investigated. While the EuF3 doping concentration is increased from 0.6% to 6.0%, the CIE (Commission Internationale de L'Eclairage) color coordinates of Eu: CaF2 crystals can be tuned from (0.28, 0.12) to (0.60, 0.38), corresponding to the luminescence color from blue to orange. XPS (X-ray Photoelectron Spectroscopy) measurements indicated that Eu2+ and Eu3+ ions both existed in the crystals. With EuF3 doping concentration increasing, the proportion of Eu3+ ions increase from 16.73% to 39.00%, while that of Eu2+ ions decrease from 83.27% to 61.00%. Moreover, the integrated intensity ratio (R) of the 614 nm to 593 nm of Eu3+ ions increase from 0.38 to 0.44, indicating the local lattice environment symmetry of Eu3+ ions become lower with higher EuF3 doping concentrations. Furthermore, the CIE chromaticity coordinates of Eu: CaF2 crystals greatly depend on the excitation wavelength. The warm white-light emission has been realized in 0.6%Eu: CaF2 crystal when the excitation wavelength is around 322 nm.