Abstract Two carbon-rich starburst gold(I) acetylide complexes [TEE][Au(PCy3)]4 (3, [TEE]H4=tetraethynylethene) and [TEB][Au(PCy3)]3 (6, [TEB]H3=1,3,5-triethynylbenzene) were prepared and their UV–vis absorption, emission and excitation spectra have been recorded. In fluid CH2Cl2 solutions, 3 exhibits prompt 1(ππ*) fluorescence with λ0–0 and λmax at 413 and 428 nm, respectively, while 6 displays 3(ππ*) phosphorescence with λ0–0 and λmax at 446 and 479 nm, respectively. The crystal structure of 3·CH2Cl2 has been determined.