A single-phase multicolor emitting phosphor, Ca3Al2O6:Ce3+,Li+, was prepared by a solid-state reaction. When the Ce3+ concentration is lower than 0.030 (molar ratio in Ca3Al2O6), yellow and greenish blue emissions can be observed under the excitation by a blue and a near UV light, respectively. The yellow-emitting phosphor possesses an internal quantum efficiency of 89%. Additional purplish blue emission turns up when Ce3+ concentrations are higher than 0.040. Tunable emission bands are originated from Ce3+ ions on different Ca sites in Ca3Al2O6. Although the emission band of purplish blue or greenish blue overlaps the excitation band of yellow emission, and the distances between the unlike Ce3+ ions are in the range of electric dipole-dipole interaction, no energy transfer is observed. Furthermore, emission wavelengths for the yellow, greenish blue, and purplish blue emission show little change upon increasing Ce3+ concentrations.