4-[(S)-2-Methylbutoxycarbonyl]phenyl 4-[(4-n-alkoxy-2,3,5,6-tetrafluorophenyl)ethynyl]benzoates have been prepared from the starting material 1-pentafluorophenyl-2-trimethylsilylacetylene. Polarizing microscope textural observation and DSC measurements of the phase transitions of these novel compounds showed that they were liquid crystals with chiral smectic C phase (S*C), smectic A(SA) and cholesteric (Ch) phases. The effects of the alkoxy chain length on the transition temperatures and enthalpies were also studied.