Our aim has been to explore the properties of cationic gold(II) complexes in the gas phase. We envisaged that the easiest general way of preparation of these complexes could start from the [(L)nAu III X2] + precursors (n = 1 for bidentate ligand L and n = 2 for monodentate ligands) that might be prone to lose a halogen radical and thereby form the desired [(L)nAu II X] + complexes (Reaction 1). In the study of the gold(III) complexes, we indeed observed this reaction path. However, we also observed competing reactions leading to the reduction of the complex to gold(I) (Reaction 2) or to the degradation of the gold(III) complex (Reaction 3).