Three series of meta-perfluoroalkylphenol esters are synthesized. Both SmA and SmC phases are identified. Their clearing points increase with increasing the perfluorocarbon chain length, while decrease with increasing the alkoxy chain length. Comparison of the 3-tridecafluorohexylbenzoates and 3-tridecafluorohexylphenol esters, the 3-tridecafluorohexylbenzoates show higher clearing points, indicating that the direction of the ester bond plays an important role in the thermostability of the liquid crystalline phases. Moreover, it was proposed that the compounds with short and long alkoxy chains packed into different structures.