Photoelectron spectroscopy and density-functional theory are combined to study the structures and chemical bonding in boron-gold alloy clusters and boron boronyl clusters: B3Aun (-) and B3(BO)n (-) (n = 1, 2). Vibrationally resolved photoelectron spectra are obtained for all four species and the B-Au and B-BO clusters exhibit similar spectral patterns, with the latter species having higher electron binding energies. The electron affinities of B3Au, B3Au2, B3(BO), and B3(BO)2 are determined to be 2.29 ± 0.02, 3.17 ± 0.03, 2.71 ± 0.02, and 4.44 ± 0.02 eV, respectively. The anion and neutral clusters turn out to be isostructural and isovalent to the B3Hn (-)∕B3Hn (n = 1, 2) species, which are similar in bonding owing to the fact that Au, BO, and H are monovalent σ ligands. All B3Aun (-) and B3(BO)n (-) (n = 1, 2) clusters are aromatic with 2π electrons. The current results provide new examples for the Au∕H and BO∕H isolobal analogy and enrich the chemistry of boronyl and gold.