The transmission spectra of LiCaAIF(6) (LiCAF) and LiSrAlF6 (LiSAF) are investigated in the ultraviolet (W) and the vacuum ultraviolet (VUV) region. The transmission edge of LiCAF (112 nm) shows almost the same value as that of LiF. Taking into account difficulties of material processing and polishing due to the cleavage or the hydroscopic nature of LiF, LiCAF is regarded as a more suitable optical material in the UV and the VUV region. Moreover, the new excitation channel around 112 nm is discovered for Ce:LiCAF crystal. This excitation is originated not from absorption of Cerium ions but from absorption around the bandgap of the host crystal.