In this paper, CaO-B2O3-2SiO2: Eu[Formula: see text] and CaO-B2O3-2SiO2: Eu[Formula: see text], Ce[Formula: see text] fluorescent glasses have been synthesized by a conventional melt-quenching method. First, under 350[Formula: see text]nm excitation, the CaO-B2O3-2SiO2: Ce[Formula: see text] luminescent glass emits light at about 400[Formula: see text]nm, and the optimum dosage is 0.3[Formula: see text]mol%. Then, under 400[Formula: see text]nm UV excitation, the CaO-B2O3-2SiO2: Eu[Formula: see text] luminescent glasses showed a strong emission with a peak around 460[Formula: see text]nm and a half wavelength of 95[Formula: see text]nm. The results showed that the luminescence of this glass was greatest when the doping amount was 0.3[Formula: see text]mol% and gradually decreased with increase of the doping amount. After calculation and analysis, it was found that this was due to the nonradiative energy transfer between Eu[Formula: see text] ions. The mechanism of energy transfer was dipole–dipole interaction. Finally, Ce[Formula: see text]/Eu[Formula: see text] co-doped luminescent glasses were also successfully prepared with strong emission. The existence of energy transfer was demonstrated by theoretical and practical measurement data. CaO-B2O3-2SiO2: Ce[Formula: see text], Eu[Formula: see text] can be used as blue fluorescent glass for white light illumination.