Three generations of dendritic poly(arylene ether)s with terminal 4-fluoraphenylthio- or 4-fluorophenylsulfonyl groups have been synthesized. A new relatively high molecular weight bisphenol containing two pendent 4-fluorophenylthio groups was converted to a poly(arylene ether sulfone) to act as the dendritic core, A divergent approach with an activation/condensation sequence was used. The pendent 4-fluorophenylthio groups in the base polymer were oxidized with H2O2 in formic acid to give 4-fluorophenylsulfonyl groups in which the fluoride groups are then activated toward nucleophilic displacement reactions. The condensation step involved the reaction of a phenol containing two pendent 4-fluorophenylthio groups with the activated core polymer in the presence of Cs2CO3. Reiteration of these steps gave the subsequent generations. The polymers have high thermal stabilities by TGA analysis (5% weight loss > 500 degreesC).