A new class of benzodioxocycloalkane-based (C8–C10) liquid crystals were prepared. The impact of ring (C8–C10) as end group was investigated. The 8–9 membered ring derivatives, 3a–3b, exhibited the nematic phases (N). The mesomorphic behaviors were weakened with increasing the size of the ring. For the ?uorinated medium ring (C8–C10) 3d–3f, it was found only the fluorinated ten membered ring 3f showed the LC phases behaviours. Modification of the ring size with different length alkyl groups and variation of the alkyl to polyfluoroalkyl markedly influenced the properties of these compounds.