A photoredox-catalyzed method for the indirect generation of acyl radicals from stable thioesters is described. The process is applicable to both aromatic and aliphatic substrates, and the resulting acyl radicals can undergo both intermolecular and intramolecular reactions. The mild reaction conditions allow for domino photoredox-catalyzed processes to occur. To illustrate the utility of the method, the total synthesis of a pharmaceutical agent is described.