Ligand exchange of phosphine-stabilized undecagold precursor particles, Au11(PPh3)8Cl3, with omega-functionalized thiols provides a convenient and general approach for the rapid preparation of large families of thiol-stabilized, subnanometer (dCORE approximately 0.8 nm) particles. The approach permits rapid incorporation of specific functionality into the stabilizing ligand shell, is tolerant of a wide range of functional groups, and provides convenient access to new materials inaccessible by other methods. Mechanistic studies and trapping experiments give insight into the progression of the ligand exchange, providing evidence that the core size of the phosphine-stabilized undecagold precursor particles is preserved during ligand exchange. The optical properties of the thiol-stabilized nanoparticles depend strongly on the composition of the ligand shell, and a series of studies suggests that this dependence is a result of the ligand shell's influence on the electronic structure of the particle core, as opposed to a structural change within the nanoparticle core.