Herein, we developed a new methodology of using aryl sulfonium salts as the aryne precursor for [3 + 2] cycloaddition reactions with azides. The reaction using readily available arenes as the feedstock features excellent atom economy, environmental friendliness and high functional group tolerance. Moreover, due to the excellent performance of the gram-scale reaction, deuterium labeling result and derivatization reactions, there are potential opportunities for large-scale production and other applications.