Two unique silver nanoclusters protected by alkynyl and diphosphine ligands have been synthesized. Single crystal structural determination reveals that they have a centered anticuboctahedral Ag13 kernel. Such a kernel is observed for the first time in a coinage metal nanocluster. This work offers new insights into the fact that the PhC[triple bond, length as m-dash]C ligand represents a new direction in synthesizing novel metal nanoclusters.