Europium doped 2CaO–P 2 O 5 –B 2 O 3 phosphors prepared via high temperature solid state reactions are reported. The evolution of luminescence and structure of the phosphors induced by variation of sintering temperature and atmosphere is investigated using photoluminescence spectra and X-ray diffraction techniques. We found that the optical performance and structure of the phosphors are sensitive to the sintering temperature and atmosphere. The luminescence intensity due to 5 D 0 → 7 F 2 transition of Eu 3+ is decreased with increasing sintering temperature. CaBPO 5 and BPO 4 crystals co-exist in the as-prepared phosphors and the relative content of these two phases is dependent on sintering temperature. CaBPO 5 crystal favors the transition of 5 D 0 → 7 F 1 of Eu 3+ ions, while BPO 4 enhances the emission of 612nm. This study gives insight into the correlation between optical properties and structure of the as-prepared phosphors. The phosphors reported here are good candidates for light emitting diode applications.