Previous electrochemical experiments showed that the reduction of gold(III) complexes often leads directly to the gold(I) complexes or that the Au III → Au II and Au II → Au I potentials are very close and therefore the steps are difficult to separate. In such a situation, where the properties of reactive complexes cannot be properly studied in solution, isolation of these species in the gas phase can extend their lifetime and thus allow a detailed study albeit in vacuum. This approach permitted an exploration of the chemistry of metal complexes in unusual oxidation states or even in the oxidation states that cannot be prepared in a condensed phase. In addition, previous DFT calculations suggested that the gold(II) complexes are more stable in the gas phase than in the solution. Herein, we present a gas-phase study of the intrinsic properties of gaseous gold(II) complexes with bidentate and tridentate ligands. We prepared the gold(II) complexes from their gold(III) precursors and explored how various common ligands stabilize the unusual oxidation state. We have characterized the prepared gold(II) complexes with gas-phase ion spectroscopy. Benchmarked to the experiment, we have also investigated their structure and spectroscopic properties by DFT calculations. [a] The complexes were generated from an acetonitrile and dichloromethane solution of the AuX3 salt (0.1 mM) and the ligand (0.1 mM) achieving a final concentration of 100 µM.