The first methodology for Au(I/III)-catalyzed oxidative cross-coupling of arenes via double C-H activation has been developed. The reaction is fully selective for the cross-coupling between electron-rich hetero-/carbocyclic arenes and electron-poor arenes bearing relatively acidic C-H bonds: The inherently high cross-selectivity of the system obviates the need for directing groups or a large excess of one of the coupling partners.