The mechanism of the gold-catalyzed oxidative cross-coupling of arenes and alkynes has been studied in detail combining stoichiometric experiments with putative reaction intermediates and DFT calculations. Our data suggest that ligand exchange between the alkyne, the Au(I)-catalyst and the hypervalent iodine reagent is responsible for the formation of both, a Au(I)-acetylide complex as well as a more reactive “non-symmetric” I(III) oxidant, responsible for the crucial Au(I)/Au(III) turnover. Further, the reactivity of the in situ generated Au(III)-acetylide complex is governed by the nature of the anionic ligands transferred by the I(III) oxidant: while halogen ligands remain unreactive, acetato ligands are efficiently displaced by the arene to yield the observed Csp2-Csp cross-coupling products through an irreversible reductive elimination step. Finally, the nature of competitive processes and catalyst deactivation pathways has also been unraveled. This detailed investigation provides insights not only on the specific features of the species involved in oxidative gold-catalyzed cross couplings but also highlights the importance of both ancillary and anionic ligands on the reactivity of the key Au(III) intermediates.