We report a joint experimental and theoretical study of the electronic and atomic structures of small gold clusters with up to 14 atoms. Well-resolved photoelectron spectra were obtained for Au-N(-) (N = 1-14) at several photon energies. Even-odd alternations were observed, where the even-sized clusters (except Au-10(-)) exhibit an energy gap between the lowest binding energy peak and the rest of the spectrum, indicating that all the neutral even-sized clusters have closed shells. The Au-10(-) spectrum reveals the existence of isomers, with the ground-state cluster exhibiting an extremely high electron binding energy. Evidence of multiple isomers was also observed in the spectra of N = 4, 8, 12, and 13. The structures of the gold cluster anions in the range N = 4-14 were investigated using first-principles simulations. A striking feature of the anionic clusters in this range is the occurrence of planar ground-state structures, which were predicted in earlier theoretical studies (Hakkinen, H.; et al. Phys. Rev. Lett. 2002, 89, 033401) and observed in ion-mobility experiments (Furche, F.; et al. J. Chem. Phys. 2002, 117, 6982) and the existence of close-lying isomers. The calculated electron detachment energies and density of states were compared with the measured data, which confirmed the ground-state structures of the anions. It is found that the main isomers observed experimentally indeed consist of planar clusters up to Au-12(-), Whereas for Au-13(-) and Au-14(-) the theoretical results from three-dimensional isomers agree better with the experiment, providing further support for the 2D to 3D structural transition at Au-12(-), as concluded from previous ion mobility experiments. We also find that small neutral clusters exhibit a tendency to form two-dimensional structures up to a size of 13 atoms.