BaCa2MgSi2O8:Eu2+ phosphors have been prepared by a conventional high temperature solid state reaction technique. The emission and excitation spectra as well as the luminescence decays were investigated, showing that Eu2+ ions enter both Ba2+ and Ca2+ sites in the host. The structural refinement reveals that about 70% Eu2+ ions occupy Ba2+ sites in samples Ba1-xEuxCa2MgSi2O8 and BaCa2(1-x)Eu2xMgSi2O8. By investigation of the thermal-quenching, the schematic energy levels for Eu2+ in BaCa2MgSi2O8 were proposed. Intense blue emission was observed under 147, 172 and 254 nm excitation in comparison with the commercial blue phosphor BaMgAl10O17:Eu2+ (BAM), demonstrating the potential application of the phosphors in plasma display panels (PDPs) and tri-color fluorescent tubes.