AbstractAromatic bisorthoesters were found to be good polymer intermediates and could be condensed with aromatic tetramines under mild conditions, in DMSO at 100°C in a relatively short reaction time to give polybenzimidazoles. The hexapropyl orthoesters of terephthalic and isophthalic acid were the preferred aromatic orthoesters because they were relatively easily purified by vacuum distillation to polymer grade intermediates, since they are liquids. Higher orthoesters distill even under good vacuum near or above the decomposition temperature of the orthoester group. Hexaethyl orthooxalate was also used and is a very useful and stable derivative of oxalic acid, which can be used for condensation reactions. These three orthoesters were used for condensations with 3,3′,4,4′‐tetraaminobiphenyl, 1,2,3,4‐tetraaminobenzene, 3,3′,4,4′‐tetraaminobiphenyl ether, and 3,3′,4,4′‐tetraaminobenzophenone. All polybenzimidazoles were obtained in high to quantitative yields and with varying molecular weights (ηinh= 0.1−0.8 dl/g), which in some cases were in