Novel, linear, high-molecular-weight single-strand heteroaromatic polymers and copolymers containing 9H-xanthene moieties in the backbone were synthesized by metal-free superacid-catalyzed stoichiometric and nonstoichiometric step-growth polymerizations of carbonyl compounds bearing electron-withdrawing substituents with bisphenols. The electrophilic aromatic substitution reactions of ketones with phenol fragments occur exclusively in ortho-positions to the hydroxy phenol group and followed by highly efficient cyclodehydration reaction of hydroxyl-containing intermediates to give corresponding substituted 9H-xanthene-2,7-diyl polymers. The polymerizations were performed at room temperature in the Brønsted superacid trifluoromethanesulfonic acid (CF3SO3H, TFSA) and in a mixture of TFSA with methylene chloride and nitrobenzene.