The crystal of 0.6at%Eu∶CaF2 and 0.6at%Eu, 6.4at%Na∶CaF2, 0.6at%Eu, 6.4at%Gd∶CaF2 were grown by porous crucible temperature gradient method. XRD results indicate that these crystals are still keeping a pure CaF2 cubic phase, and the absorption intensity decreases after co-doping. The fluorescence spectrum of the crystal material excited by 398 nm xenon lamp shows that the luminescence intensity of Eu2+ at 424 nm could significantly increases after the co-mixing of ions, while the characteristic emission of Eu3+ 5D0→7FJ(J=1,2,3,4) shows no obvious change either in peak position or intensity except for a broadening of full width at half maximum (FWHM). The emissions of 5D2→7F3 and 5D0→7F0 transitions in 0.6at%Eu, 6.4at%Gd∶CaF2 are mainly due to the fact that the inversion center lattice is broken after co-doped Gd3+, and the R value (electric and magnetic dipole transition ratio) significantly reduces, which improves the symmetry of crystal lattice structure. After co-doping Na+, the coordinates of CIE color gamut changes from (0.303 7, 0.142 5) to (0.204 3, 0.062 6), corresponding to the gamut regulation from purple to blue.