During photoelectron spectroscopy experiments, the spectra of B11O- and B10Au- clusters are found to exhibit similar patterns except for a systematic spectral shift of similar to 0.5 eV, hinting that they possess similar geometric structures. The electron affinities are measured to be 4.02 +/- 0.04 eV for B11O and 3.55 +/- 0.02 eV for B10Au. DFT calculations at the B3LYP level show that B11O- and B10Au-adopt similar C-1 ((1)A) ground states, which are based on the quasiplanar B-10 cluster interacting with a BO unit and Au, respectively. The B11O- and B10Au- clusters are thus valent isoelectronic because both BO and Au can be viewed as monovalent units, forming highly covalent B-BO and B-Au bonds analogous to the B-H bond in B10H-. For B10Au-, we also find a highly symmetric D-10h ((1)A(1g)) planar molecular wheel as a minimum on the potential energy surface. However, it is 45 kcal/mol above the ground state at the B3LYP level and not viable for experimental observation. Natural bond orbital analyses reveal interesting covalent versus ionic B-Au bonding in the C-1 B10Au- and D-10h B10Au- structures, respectively, providing insight for the design of D-nh MBn molecular wheels.