A facile method for the direct cross-annulation of unfunctionalized tetracene is reported. The one-pot oxidative cross-dehydrogenative coupling (CDC) between tetracene and aromatic compounds, such as benzene or 2-methylthiophene, furnished annulated products with an extended π-network. Moreover, relative to the benzo-annulated tetracenes, thieno-annulated tetracenes exhibited notably improved photooxidative