Photoluminescence and scintillation properties of Cu-doped LiCl single crystals synthesized by the Bridgman-Stockbarger method were evaluated. Under UV and X-ray irradiation, two emission bands were observed at 325 and 400 nm, and these emissions would be due to 3d⁹4s¹-3 d¹⁰ transition of Cu⁺ and Cu⁺ perturbed by near OH⁻, respectively. From pulse height spectra under ²⁵²Cf neutron irradiation, the 0.1% Cu-doped sample showed the highest light yield (LY) of 5600 photons/neutron among all the samples and the energy resolution of 8.3 %. The LY and the energy resolution of 0.1% Cu-doped LiCl single crystal were comparable with those of commercial Li-glass (GS20). Furthermore, Cu-doped LiCl was not sensitive to γ-ray, and neutron-γ discrimination performance of 0.1% Cu-doped LiCl single crystal was better than that of GS20.