The phosphane-stabilized gold cluster [Au(13)(PMe(2)Ph)(10)Cl(2)](3+) was studied using density functional theory. The extraordinary stability of the cluster has been attributed to the stability of the gold core and the protection conferred by ligands. Here, five stability factors of the gold core were explained and verified by investigating the Au (13) (5+) core in detail. Interactions between the gold core and several PR(3) ligands (R = Me, H, I, Br, Cl, F) were investigated according to the different electron donor abilities of each ligand; bonding energy between the ligand and the gold core was found to increase with the electronegativity of the R substituent. Furthermore, two other aspects of the ligands were clarified: how the ligand stabilizes the Au (13) (5+) core, and which kind of ligand provides the best stabilization for the cluster.