The total structure determination of thiol-protected Au clusters has long been a major issue in cluster research. Herein, we report an unusual single crystal structure of a 25-gold-atom cluster (1.27 nm diameter, surface-to-surface distance) protected by eighteen phenylethanethiol ligands. The Au-25 cluster features a centered icosahedral Au-13 core capped by twelve gold atoms that are situated in six pairs around the three mutually perpendicular 2-fold axes of the icosahedron. The thiolate ligands bind to the Au-25 core in an exclusive bridging mode. This highly symmetric structure is distinctly different from recent predictions of density functional theory, and it also violates the empirical golden rule-cluster of clusters", which would predict a biicosahedral structure via vertex sharing of two icosahedral M-13 building blocks as previously established in various 25-atom metal clusters protected by phosphine ligands. These results point to the importance of the ligand-gold core interactions. The Au-25(SR)(18) clusters exhibit multiple molecular-like absorption bands, and we find the results are in good correspondence with time-dependent density functional theory calculations for the observed structure.