A series of N-heterocyclic carbene-based Au I -σ-acetylide complexes of the type [(Bimz)Au-CϵCR] (Bimz = benzimidazolin-2-ylidene; R = aryl, silyl groups) (1a-1l, 2, 3) were prepared from the precursor [(Bimz)Au I Cl] by an in situ deprotonation of the terminal alkynes. Steady-state photoluminescence studies revealed that most of these complexes exhibit phosphorescence at room temperature and in 77 K rigidified matrices. Molecular structures were determined by single-