The fluorocarbon derivatives were synthesized. Liquid crystalline states were studied by DSC and microscopic observation. T-NI of those compounds were from 161.2 degrees C to 191.7 degrees C, which represented those compounds had very good liquid crystalline stability. Smectic C temperature range was 91.7 degrees C for F8H2OPMB, 54.9 degrees C for F8H2OPCB, 41.1 degrees C for F8H2OPMB-F, 36.2 degrees C for F8H2OMB, 27.4 degrees C for F8H2OPCB-F, and 10.8 degrees C for F6H2OMB. The structures of F8H2OPCB and F8H2OPCB-F at room temperature were tilted herringbone packing of two aromatic ring ester cores (smectic K phase) and perfluoroalkyl chains were located up and down alternatively. Smectic K was proved by high intensity of 003 and 004 reflections in X-ray diffraction.