A large thiolate/phosphine coprotected Ag-50(Dppm)(6)(SR)(30) nanocluster was synthesized through the further growth of Ag-44(SR)(30) nanocluster and characterized by X-ray photoelectron spectroscopy (XPS), electrospray ionization mass spectrometry (ESI-MS), and single-crystal X-ray analysis. This new nanocluster comprised a 32-metal-atom dodecahedral kernel and two symmetrical Ag-9(SR)(15)P-6 ring motifs. The 20 valence electrons correspond to shell closure in the Jellium model. Moreover, this nanocluster could be alloyed by templated/galvanic metal exchange to the homologue AuxAg50-x(Dppm)(6)(SR)(30) nanocluster; the latter showed much higher thermal stability than the Ag-50(Dppm)(6)(SR)(30) nanocluster. Further experiments were conducted to study the optical, electrical, and photoluminescence properties of both nanoclusters. Our work not only reports two new larger size nanoclusters but also reveals a new way to synthesize larger size silver and alloy nanoclusters, that is, controlled growth/alloying.