We investigate BS2(-) and BSO(-) clusters using photoelectron spectroscopy and theoretical calculations. The electron affinities of BS2 and BSO are measured to be 3.80 ± 0.03 and 3.88 ± 0.03 eV, respectively, higher than those of halogen atoms. Thus, BS2 and BSO can be considered as superhalogens. The comparison of experimental and theoretical results confirmed that the ground state structures of BS2(-), BSO(-), and their neutrals are all linear. Analyses of natural bond orbitals suggest that both BS2(-) and BSO(-) have dual 3c-4e π hyperbonds.