Two kinds of new aromatic poly(arylene ether)s containing sulfonic acid groups were synthesized. Polymer 1 composed of tetraphenylphenylene ether and perfluorobiphenylene units was sulfonated with chlorosulfonic acid. Sulfonation took place only at the para position of the pendant phenyl rings. The average degree of sulfonation per repeating unit (m) was controlled from 1 to 4. Sulfonated polymer 2 with m = 3 was soluble in methanol and dimethyl sulfoxide and swelled in water. Incorporating bis(3,5-dimethylphenyl)sulfone moieties into the sulfonated polymer imparts less methanol affinity. Polymers 4 with 30-65 mol % tetrakis(sulfophenyl)phenylene ether units has high decomposition temperatures above 300 degreesC, hydrophilicity, and good hydrolytic stability.