Although aryl chlorides are among the most abundant and stable aromatic electrophiles, the coupling of aryl chlorides with isocyanides has remained an unsolved challenge. Herein, we report a general transformation of aryl chlorides, isocyanides, and thiocarboxylates to synthesize thioamides. The sterically hindered and electron-rich Josiphos ligand significantly facilitates the rate-determining oxidative addition step and reduces the toxicity of isocyanides toward the metal center. The combination of thiocarboxylate as the nucleophile and Josiphos as the ligands enabled the coupling-tolerated various 1°, 2°, and 3° isocyanides, which provides a rapid, efficient, and versatile method for the synthesis of large quantities of thioamides, including those of pharmaceutical relevance.