The dinuclear Pt–Au complex [(CNC)(PPh₃)Pt Au(PPh₃)](ClO₄) (2) (CNC=2,6-diphenylpyridinate) was prepared. Its crystal structure shows a rare metal–metal bonding situation, with very short Pt–Au and Au–C_ipso(CNC) distances and dissimilar Pt–C_ipso(CNC) bonds. Multinuclear NMR spectra of 2 show the persistence of the Pt–Au bond in solution and the occurrence of unusual fluxional behavior involving the [Pt^II] and [Au^I] metal fragments. The [Pt^II]⋅⋅⋅ [Au^I] interaction has been thoroughly studied by means of DFT calculations. The observed bonding situation in 2 can be regarded as a model for an intermediate in a transmetalation process.