This study reports on the crystal growth, luminescence, and scintillation performance of a novel elpasolite K2LiCeCl6 scintillator. The single crystal of this material was grown by the two-zone vertical Bridgman technique. The luminescence and scintillation performance were studied under X-, γ-rays, and α-particles excitation at room temperature. The fast scintillation response and α-particles and γ-ray separation capability reveal that this scintillator can be used as a dual-mode γ-rays and thermal neutron detector.