A combustion synthesis method has been developed for synthesis of Eu2+ doped CaAlSiN3 phosphor and its photoluminescence properties were investigated. Ca, Al, Si, and Eu2O3 powders were used as the Ca, Al, Si and Eu sources. The addition of NaN3, NH4Cl and Si3N4 powders was found to increase significantly the product yield. These powders were mixed and pressed into a compact, which was then wrapped up with an igniting agent (i.e., Mg+Fe3O4). The compact was ignited by electrical heating under a N2 pressure of ≤1.0 MPa. Effects of these experimental parameters on the product yield were investigated and a reaction mechanism was proposed. The synthesized CaAlSiN3:Eu2+ phosphor absorbs light in the region of 200–600 nm and shows a broad band emission in the region of 500–800 nm due to the 4f65d1 → 4f7 transition of Eu2+. The sample doped with Eu2+ at the optimized molar ratio of 0.04 is efficiently excited by the blue light (460 nm) and generates emission peaking at ~650 nm with peak emission intensity ~106% of a commercially available phosphor, YAG:Ce3+(P46-Y3).The internal quantum efficiency of the synthesized phosphor was measured to be 71%, compared to 69% of the YAG:Ce3+ (P46-Y3).