The difunctionalization of alkenes using aryl thianthrenium salts as the aryl sources has been reported sporadically. However, the four-component difunctionalization of alkenes on the basis of aryl thianthrenium salts has not been reported thus far and still remains a challenge. Herein, a visible light/copper catalysis-enabled four-component reaction of aryl thianthrenium salts, DABCO·(SO2)2, alkenes, and TMSN3 is presented, which affords a facile approach to β-azidosulfones in good yields with broad substrate scope and excellent functional group tolerance. This strategy indirectly realizes the method for the synthesis of β-azidosulfones through site-selective aryl C-H bond functionalization and alkene difunctionalization. This developed method is an important complement to thianthrenium salts chemistry.