Novel luminescent liquid crystals were synthesized by introducing a mesogenic cyanobiphenylyl side chain to a luminescent naphthalene core. The 1,5-naphthalene derivatives were thermotropic liquid crystals showing monotropic phase transition, while 2,6-naphthalene derivatives showed an enantiotropic behavior. All compounds had an intense bluish emission in the solid, liquid crystal, and isotropic liquid states, which was investigated by UV-vis and PL spectroscopies.