This work reports a Cu‐catalyzed coupling technique for synthesizing (E)‐dienyl sulfones and β‐chlorosulfones from 1‐arylbutadienes and styrenes, respectively. By employing easily available and inexpensive reagents, this method enables the synthesis of a diverse array of dienyl sulfones and β‐chlorosulfones with excellent functional group tolerance under base‐ and oxidant‐free conditions. It also proves versatile for the late‐stage functionalization of drug molecules and the scale‐up reactions. The method showcases notable selectivity, gentle reaction conditions, and compatibility with various functional groups as demonstrated through 66 examples with excellent display of regioselectivity.