Novel pyrrones were synthesized by one-stage polycondensation in polyphosphoric acid of 2,3,5,6-tetraamino-l,4-benzoquinone with pyromellitic anhydride, 3,3′,4,4′-benzophenonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, or 3,4,9,10-perylenetetracarboxylic dianhydride. The prepared polymers showed a considerable percentage of imide linkages, so they were heated at 350°C under high vacuum to increase the ring closure to the pyrrone structure. The polymers were insoluble in all common polar aprotic solvents, even in dimethylacetamide-water mixture, after reduction with sodium dithionite, but were slightly soluble in concentrated sulfuric and methanesulfonic acid. The thermal decomposition of the polymers (weight loss 5%) started above 400°C both under nitrogen and in air.