<p>The concept of superatoms has long been used as a guide to understand the stability of clusters. However, little work has been done to compare the structural stability of ligand-protected Ag nanoclusters with the same kernel using the superatom concept. In this study, we construct six clusters based on the same Ag₁₃ kernel, including 5<i>e</i> Ag₁₇(SR)₁₂, 6<i>e</i> Ag₂₀(SR)₁₄, 6<i>e</i> Ag₁₈(SR)₁₂, 7<i>e</i> Ag₁₉(SR)₁₂(DMPA)₃, 7<i>e</i> Ag₂₅(SR)₁₈, and 8<i>e</i> [Ag₂₅(SR)₁₈]^– (where R = -CH₃, Methyl; DMPA = C₆H₁₆P₂, 1,2-Bis(dimethylphosphino)ethane). The regulation of the valence electron count is achieved by varying the outer motifs—Ag(SR)₂, Ag₂(SR)₃, Ag(SR)₃, and Ag₂(SR)₄(DMPA)—which withdraw 1, 1, 2, and 2 valence electrons from the inner kernel, respectively. The results show that the 8<i>e</i> [Ag₂₅(SR)₁₈]^– cluster, with its closed 1S²|1P⁶ electron configuration, exhibits the least structural variation, a more balanced atomic charge distribution in the kernel Ag atoms, and a relatively large HOMO-LUMO gap. This work contributes to a better understanding of the superatom concept in the context of the structure of ligand-protected Ag nanoclusters.</p>