HCl in solution accepts electron density from Au NPs and partially reduces at room temperature, as occurs with other simple diatomic molecules, such as O2 and H2 . The activation can be run catalytically in the presence of alkynes to give exclusively E-vinyl chlorides, after the regio- and stereoselective transfer of HCl. Based also on this method, vinyl chloride monomer (VCM) can be produced in a milder and greener way than current industrial processes.