A series of novel, linear, soluble, high‐molecular‐weight, fluorinated aromatic polymers has been obtained for the first time using a superacid‐catalyzed polyhydroxyalkylation reaction of fluorinated carbonyl‐containing compounds: 1,1,1,‐trifluoroacetone (1), 2,2,2‐trifluoroacetophenone (2), 2,3,4,5,6,‐pentafluorobenzaldehyde (3), and octafluoroacetophenone (4) with aromatic hydrocarbons such as biphenyl (a), phenyl ether (b), terphenyl (c), and 4,4′‐diphenoxybenzophenone (d). These Friedel‐Crafts‐type aromatic electrophilic substitution reactions are performed at room temperature in trifluoromethane sulfonic acid or in its mixtures with dichloromethane. The polymers obtained are soluble in common organic solvents, and colorless transparent films could be cast from the solutions. 1H and 13C NMR analyses of the polymers synthesized reveal their linear, highly regular structure. The polymers also possess high thermostability.