1-(Perfluoroalkylethyl-X)-4-alkoxybenzenes (X = thio for 1-m,n and X = sulfonyl for 2-m,n) were synthesized as a new class of rod-shaped organic gelators without hydrogen-bonding groups. Compounds 1-m,n and 2-m,n form gels in several polar solvents to give physical gels. The gel-sol transition temperatures of propylene carbonate gels were about 30 °C80 °C, depending on the chemical structures of the compounds. The formed gels consist of fibrous structures.