Described herein is a facile, one‐step synthesis of 5‐substituted thieno[3,4‐c]pyrrole‐4,6‐diones (TPDs) by a palladium‐catalyzed carbonylative amidation of commercially available dibromoaryl compounds under mild conditions. TPDs are important structural components for organic electronics. Our optimal conditions afforded the desired 5‐n‐octyl‐TPD in a 63 % yield in one step. This is a considerably improved process compared with the most conventional approach (5 steps in 12–22 %) In addition, this method was applied to the syntheses of pyridinopyrroledione (PPD) and pyrroloisoindoletetraone (PIT), which also are important structural components for various functional materials and bioactive compounds. The developed synthetic approach would be a valuable aid to the materials and drug discovery process.