Efficient synthesis of atomically precise phosphine-capped gold nanocluster (with >10 metal atoms) is important to deeply understand the relationship between structure and properties. Herein, we successfully utilize the thiol-induced synthesis method and obtain three atomically precise phosphine-protected gold nano clusters. Single-crystal X-ray structural analysis reveals that the nanoclusters are formulated as [Au-13(Dppm)(6)](BPh4)(3), [Au-18(Dppm)(6)Br-4](BPh4)(2), and [Au-20(Dppm)(6)(CN)(6)] (where Dppm stands for bis(diphenylphosphino)methane), which are further confirmed by electrospray ionization mass spectrometry, thermogravimetric analysis, and X-ray photoelectron spectroscopy. Meanwhile, [Au-18(Dppm)(6)Br-4] (BPh4)(2) could be converted into [Au-13(Dppm)(6)](BPh4)(3) and [Au-20(Dppm)(6)(CN)(6)] by engineering the surface ligands under excess PPh3 or moderate NaBH3CN, respectively. Furthermore, according to the different binding ability of silver with halogen, we successfully achieved target metal exchange on [Au-18(Dppm)(6)Br-4] (BPh4)(2) with Ag-SAdm (where HS-Adm stands for 1-adamantane mercaptan) complex and obtained [AgxAu18-x(Dppm)(6)Br-4](BPh4)(2) (x = 1, 2) alloy nanoclusters. Our work will contribute to more intensive understanding on synthesizing phosphine-protected nanoclusters as well as shedding light on the structure-property correlations in the nanocluster range.