A series of gold(I) complexes featuring a novel ligand–gold–ynaminyl architecture was synthesized and characterized. The incorporation of a (carbazolyl)ethynide (C≡C-Cbz) ligand connects the photonic functionality of the carbazolyl with the N-heterocyclic carbene (NHC) through a long ethynide-Au bridge, showing shorter radiative lifetimes and higher E_T values in solution in comparison to their carbene–metal–amido (CMA) congeners. The photophysical properties of the NHC complexes reveal a broad UV emission band when measured at room temperature and a hidden phosphorescence band with high quantum yield (up to 94%) at 77 K. This new photonic functional group based on polar ynamines is presented as a versatile platform for the design of high-energy gold-based luminophores with applications in photocatalysis.