A series of Ce3+ and Mn2+ co-doped LiCaB O 3 single composition phosphors were synthesized by a solid-state reaction method, and their luminescent properties had also been investigated. Ce3+ and Mn2+ co-doped LiCaB O3 phosphors showed a blue and orange dual emission under the near-UV light excitation within the wavelength range of 325-375 nm, resulting from the 5d-4f transitions of Ce3+ and the d-d forbidden transition of Mn2+, respectively. The energy transfer from Ce3+ to Mn2+ was investigated and demonstrated to be a resonance-type via a dipole-dipole mechanism with the critical distance of about 4.1 Å. The photoluminescence intensity ratio of blue and orange emission could be tuned by adjusting the concentration of Ce3+ and Mn2+. The potential applications of these dual-emitting phosphors are the alternative blue and orange-emitting light emitting diode (LED) conversion phosphors due to their strong excitation bands in the wavelength range of 325-375 nm.