A series of blue-emitting NaCaBeSi2O6F:Eu2+ phosphors were obtained via a solid state reaction. NaCaBeSi2O6F:Eu2+ exhibit a broad absorption from 250 to 450 nm when monitored at 467 nm and display a broad emission band from 400 to 600 nm when excited at 397 nm. The concentration quenching was obtained when the concentration of Eu2+ was increased to 0.8 mol%. Energy transfer interactions between Eu2+ in host is due to dipole-dipole mechanisms and the critical distance was calculated to be 31.96 angstrom. The results obtained in this study highly indicates that NaCaBeSi2O6F:Eu2+ can be a potential blue-emitting phosphor for light quality improvement in white-LED applications.