We present a rare intramolecular Au···H-C(sp3) hydrogen-bonding interaction and luminescent properties of a gold(I) carbene complex. The Au(I) complex [(L)Au(I)Cl] (1), where L = N-(9-anthracenyl)-N′-(heptyl)benzimidazol-2-ylidene, was prepared, and thermal, emission, and lifetime properties along with a density functional theory study have been considered. X-ray diffraction analysis of single crystals evidenced the solid-state structure of gold complex 1, which exhibited the expected linear coordination geometry. The n-heptane arm of L modulates the hydrogen-bonding interaction between Au(I) and the hydrogen atom of one of the CH2 moieties. The packing of the gold(I) carbene complex shows an interesting one-dimensional column in the solid state due to intermolecular Cl···H interactions. The blue emission of 1 in the 400-560 nm region has been tentatively ascribed to arise from intraligand and gold transitions, but the hydrogen-bonding interactions may also make partial contributions. Copyright © 2020 American Chemical Society.