This paper describes the synthesis of and mesomorphic property and gelation ability for 2-Alkoxy- 6-[4-(2-perfluorohexyl)ethylthiophenyl]naphthalene (compounds 1-n). Compounds 1-n show exclusively a smectic A (SmA) phase, where the SmA-isotropic phase transition temperatures are 192 degrees C for 1-1 and 171 degrees C for 1-6. The SmA phase is characterized using a polarized microscope and DSC measurements. Interestingly, compounds 1-n form physical gels (thermo-reversible gels) in n-octane, ethanol, and aprotic polar solvents such as acetonitrile and -butyrolactone, where the sol-gel transition temperatures are 60 degrees C for 1-1 and 80 degrees C for 1-6. The propylene carbonate gel is characterized by scanning electron microscope (SEM) observation, showing nano-fibers assembled with compound 1-6.