Non-noble metals catalyzed carbonylative reactions serve as straightforward and sustainable methods for the synthesis of functionalized carbonyl-containing compounds. Herein, a low-valent-tungsten-catalyzed reaction that enables the coupling of aryl iodides and alcohols or phenols was disclosed, employing the readily available W(CO)6 as the effective catalyst and PPh3 as ligand. Under the optimal reaction conditions, aryl iodides smoothly underwent carbonylative coupling reactions with alcohols or phenols, processing the feature of broad substrate scope and good functional groups tolerance. Furthermore, this conversion can be carried out on a gram scale, showcasing significant promise in the synthesis of pharmaceutical or biologically active compounds.