In this study, Sr2+, Ca2+, Zn2+, and Mg2+ ions act to tune the emission band to the blue-cyan region in BaxSryB2O5:Ce3+ (BSBO), BaxCazB2O5:Ce3+ (BCBO), BaxZnuB2O5:Ce3+ (BZBO), and BaxMgvB2O5:Ce3+ (BMBO) phosphors. A red shift occurs with the increase of Sr2+, Ca2+, Zn2+, and Mg2+ concentration, and a blue shift occurs when the concentrations of Sr2+, Ca2+, Zn2+, and Mg2+ exceed the critical value. The emission color can be tuned from deep blue (0.15, 0.12) to cyan (0.16, 0.27) upon 365 nm UV lamp excitation due to the crystal field splitting and centroid shifts. The excitation band shift to long wavelength by introducing ions, so that the synthesized phosphor can be better matched with the n-UV chip. The emission intensity slowly decreases with the temperature increasing. Therefore, the BMBO:Ce3+, BZBO:Ce3+, BCBO:Ce3+, and BSBO:Ce3+ phosphors with relatively good thermal stability were synthesized, which could have potential applications in the n-UV white LEDs.