Novel blue-emitting borofluoride phosphors Ba3Sr4(BO3)(3)F-5: Ce3+, Na+ were synthesized via high-temperature solid-state reactions. The crystal structure, luminescent properties and concentration quenching of the phosphors, as well as their luminescent thermal quenching capabilities were investigated firstly. The theoretical calculation indicated that the dipole-dipole interaction was dominantly involved in the mechanism of concentration quenching of Ce3+ in the phosphors, and the critical distance (R-c) calculated by quenching concentration and spectral overlap method were 28.32 and 26.25 angstrom, respectively. The composition-optimized Ba3Sr4(BO3)(3)F-5: 0.03Ce(3+), 0.03Na(+) exhibited the preferable CIE coordinates of (0.151, 0.057) at a correlated color temperature of 2654 K, whose color purity was better than that of the commercial blue phosphor BaMgAl10O17: Eu2+. In view of its strong absorption in the UV region, novel blue emission peaking at 422 nm, and suitable thermal luminescence stability, the Ce3+-doped Ba3Sr4(BO3)(3)F-5 phosphor can serve as a potential new material for phosphor-converted light-emitting diodes (LEDs). (c) 2013 Elsevier Ltd. All rights reserved.