Thermotropic liquid crystals with fluorocarbon chains have attracted much attention, because they are feasible to form smectic phases. Herein, two series of chiral compounds with semiperfluorocarbon chains were designed and synthesized. These compounds were characterized by IR, H-1 NMR, F-19 NMR, mass spectroscopy, and elemental analysis. Phase transition behavior was investigated by differential scanning calorimetry and polarized optical microscopy. Members of the two-ring series do not exhibit liquid crystalline phases. However, the three-ring analogues exhibit an enantiotropic SmA phase. When the length of alkyl chains is sufficient, an enantiotropic SmB phase is also identified.