As demonstrated herein, the ligand exchange chemistry of phosphine-stabilized Au11 clusters with ω-functionalized thiols is a powerful synthetic method that provides convenient access to a diverse family of functionalized Au11 clusters. The general nature of the presented ligand exchange approach, in combination with the ease preparation, makes this approach of broad utility. The approach is general and shows the high tolerance for a wide variety of functional groups. Mechanistic studies provided conclusive evidence that the Au11 core of the precursor particle remains intact during ligand exchange and showed that the ligand exchange of these particles follows a different pathway than for ligand exchanges of larger gold nanoparticles such as “Au101(PPh3)21Cl5”. Optical studies of the products show a strong dependence on the nature of the stabilizing thiol ligands.