A series of gold(I)−carbene complexes of the type [Au(R2-bimy)L] (R = Et, Me; bimy = benzimidazol-2-ylidene; L = Cl, Br, I, bimy, thiophenolate, phenylacetylide) have been prepared. These carbene complexes are luminous in acetonitrile solution and in the solid state with long lifetimes at room temperature. Multiple emissions have been observed for different R and L. The crystal structure of [Au(Me2-bimy)Cl] shows a relatively short intermolecular AuI−AuI contact of 3.1664(10) Å and an intermolecular ring π−π interaction with a ring−ring distance of 3.45 Å. The structure of [Au(Et2-bimy)Cl], however, shows only intermolecular ring−ring interactions with a distance of 3.53 Å. Crystal structure data suggest that bimy is a high-trans-influence ligand.