Ligand-free metal clusters can be prepared over a wide size range, but only in comparatively small amounts. Determining their size-dependent properties has therefore required the development of experimental methods that allow characterization of sample sizes comprising only a few thousand mass-selected particles under well-defined collisionfree conditions. In this review, we describe the application of these methods to the geometric structural determination of Au + n and Au − n with n = 3-20. Geometries were assigned by comparing experimental data, primarily from ion-mobility spectrometry and trapped ion electron diffraction, to structural models from quantum chemical calculations.