This paper describes preparation and physico-chemical properties of 1-alkoxy-4-(2-perfluoroalkyl)ethoxybenzenes (FmOOCn). For FmOOCn, 4-F(CF2)(m)CH2CH2O-phenyl-O-(CH2)(n)H, three homologues, m = 8 (n = 1, 2) and m = 10 (n = 1) reveal monotropic smectic A and unidentified smectic phases, respectively. Simultaneously, most of the homologous are possible to gelatinize various organic solvents such as octane, cyclohexane, DMF, ethanol, and so on. The gelation ability increases with increasing the carbon number of the perfluoroalkyl chain. The formed gel is transparent, semitransparent or opaque, and the phase transition between the gel phase and the isotropic fluid is thermally reversible. The images of gel observed with scanning electron microscope (SEM) show gathered fibrous aggregates.