S²⁻, MoO₄²⁻, and Mo₆O₂₂⁸⁻ were successfully employed as templates in the formation of six high-symmetry polynuclear silver clusters as exemplified in the single-crystal X-ray structures of [S@Ag₁₈(^tBuC₆H₄S)₁₆(dppp)₄]·DMF·5CH₃CN·3CH₃OH (1), [MoO₄@Ag₂₄(MeC₆H₄S)₁₂(dppm)₆(MoO₄)₄]·2BF₄·C₂H₅NO (2), [MoO₄@Ag₂₄(MeC₆H₄S)₁₂(dppm)₆(MoO₄)₄]·2CF₃SO₃ (3), [MoO₄@Ag₂₄(MeC₆H₄S)₁₂(dppf)₆(MoO₄)₄]·2CF₃SO₃ (4), [MoO₄@Ag₂₄(MeC₆H₄S)₁₂(dppb)₆(MoO₄)₄]·2CF₃SO₃ (5) and [Mo₆O₂₂@Ag₄₆(^tBuC₆H₄S)₃₂(dppm)₄(CH₃CN)₈]·6CF₃SO₃ (6) (dppp = 1,3-bis(diphenylphosphino)propane, dppm = bis(diphenylphosphino)methane, dppf = 1,1′-bis(diphenylphosphino)ferrocene and dppb = 1,4-bis(diphenylphosphino)butane). Cluster 1 is a S²⁻-centered octadecanuclear banana-shaped molecule. Clusters 2–5 have similar structures consisting of a tetrahedron of a MoO₄²⁻ core and four MoO₄²⁻ where three silver atoms cap each face and a pair sits on each edge, giving tetraicosanuclear ball-shaped molecules. Although different diphosphine ligands and silver salts were used in the syntheses, 2–5 contain a common building cluster unit with similar geometry and nuclearity. With (Bu₄N)₂Mo₆O₁₉ as a template, a giant 46-silver-atom cluster encapsulates an in situ modified Mo₆O₂₂⁸⁻ unit. The nuclearity and geometry depend on the size and shape of the templates. High-resolution electrospray mass spectrometry (HR-ESI-MS) analyses of 4 indicate its exceptionally high stability in acetonitrile. The solid-state luminescence of 1 as a function of the temperature exhibits thermochromism from red to yellow due to the different intensities of the two bands. This work established a new strategy for the construction of polynuclear silver clusters using an anionic template and mixed S- and P-donor ligands where a promising approach for building novel dual emissive materials is unraveled.