By adopting the interplay between ligand-enabled Au(I)/Au(III) catalysis and the unique π-activation mode of gold complexes, a highly coveted 1,2-heteroarylation of alkenes has been accomplished. The present ligand-enabled approach not only circumvents the requirement for strong sacrificial oxidants or photocatalysts but also operates under mild reaction conditions by utilizing simple and non-prefunctionalized aryl coupling partners.