An efficient method for synthesizing thioester compounds under metal‐free conditions was reported. Thus, a series of indole‐substituted thioesters were easily obtained in the presence of PhICl2 (dichloroiodo‐benzene) starting from N‐arylthiocarbamates and indoles. This Newman‐Kwart‐type rearrangement reaction features metal free, base free, mild reaction conditions, good functional tolerance, and good yield, showing potential value for preparing some biologically and pharmaceutically active compounds. In the presence of PhICl2, a series of thioester compounds containing indole structures were obtained starting from indoles and the masked thiols (N‐arylthiocarbamates). This method has the advantage of easily available starting material, metal and base‐free, simple operation, mild reaction conditions, and produces good yields.