Na co-doped Eu: LiCaAlF6 (Eu, Na: LiCAF) single crystals were grown by the micro-pulling-down (mu-PD) method, and their optical and scintillation properties were examined to reveal the effects of the Na co-doping. The crystals were single-phase materials demonstrating structure isomorphic with that of undoped LiCAF. To perform the crystals characterization, the specimens with dimensions of several millimeters were cut from highly transparent and crack free fragments of the crystals and polished. It was observed that Na co-doping resulted modification of the transmittance and the excitation spectra, and increased the light yield detected under neutron irradiation.