Carbonylation of aryl electrophiles is an important method for constructing aromatic carbonyl compounds for materials science and pharmaceutical applications. However, there have been few studies on the carbonylation of abundant, inexpensive aryl chlorides. Moreover, the existing carbonylation methods usually require a high temperature, control of the CO pressure, and structurally complex catalysts and ligands. We herein report a mild, operationally simple method for visible-light-triggered amino- and alkoxycarbonylation of inert (hetero)aryl chlorides with Mn2(CO)10 as both a catalyst and solid CO source at room temperature. This method, which does not require external metal catalyst, photosensitizer, or CO gas, is also suitable for other coupling partners, including aryl bromide and iodide, phenol, or arylamine derivatives.