Luminescent naphthalene-based liquid crystals were newly synthesized and changes of the luminescent color through the phase transitions were characterized. We prepared the compounds by combining naphthalene and known mesogenic cores, oxadiazole and fluorocyanobiphenyl, using methylene spacers. Both oxadiazole-naphthalene and fluorocyanobiphenyl-naphthalene series showed bluish luminescence in all phases. Among them, the emission peaks of 3-fluoro-4-cyano-4 '-[8-(6-hexyloxy-2-naphthyloxy)octyloxy]biphenyl in the liquid crystal and isotropic liquid states showed significant red shifts compared to that in the crystal state, which was due to specific interaction between the electron rich naphthalene and electron deficient fluorocyanobiphenyl cores.