Using the conventional high temperature solid-state reaction method Ba2Ca(PO4)2:Eu2+ phosphors were prepared. The phase structure, photoluminescence (PL) properties, and the PL thermal stability of the samples were investigated, respectively. Under the excitation at 365nm, the phosphor exhibited an asymmetric broad-band blue emission with peak at 454nm, which is ascribed to the 4f5d transition of Eu2+. It was further proved that the dipoledipole interactions results in the concentration quenching of Eu2+ in Ba2Ca1x (PO4)2:xEu2+ phosphors. When the temperature turned up to 150 degrees C, the emission intensity of Ba2Ca0.99(PO4)2:0.01Eu2+ phosphor was 59.07% of the initial value at room temperature. The activation energy E was calculated to be 0.30eV, which proved the good thermal stability of the sample. All the properties indicated that the blue-emitting Ba2Ca(PO4)2:Eu2+ phosphor has potential application in white LEDs.