Negatively charged sodium auride clusters, NanAun- (n = 1-3), have been investigated experimentally using photoelectron spectroscopy and ab initio calculations. Well-resolved electronic transitions were observed in the photoelectron spectra of NanAun- (n = 1-3) at several photon energies. Very large band gaps were observed in the photoelectron spectra of the anion clusters, indicating that the corresponding neutral clusters are stable closed-shell species. Calculations show that the global minimum of Na2Au2- is a quasi-linear species with C-s symmetry. A planar isomer of D-2h symmetry is found to be 0.137 eV higher in energy. The two lowest energy isomers of Na3Au3- consist of three-dimensional structures of C-s symmetry. The global minimum of Na3Au3- has a bent-flake structure lying 0.077 eV below a more compact structure. The global minima of the sodium auride clusters are confirmed by the good agreement between the calculated electron detachment energies of the anions and the measured photoelectron spectra. The global minima of neutral Na2Au2 and Na3Au3 are found to possess higher symmetries with a planar four-membered ring (D-2h) and a six-membered ring (D-3h) structure, respectively. The chemical bonding in the sodium auride clusters is found to be highly ionic with Au acting as the electron acceptor.