Using polyhedral oligomeric silsesquioxane (POSS) modified by a thiol group as a protected ligand, atom‐precise multi‐heteorocluster‐based dendrimers Ag12@POSS6 (1 a and 1 b) were assembled. Through the reactive −SH groups, six POSS shell ligands stabilize the central 12‐core silver(I) cluster by diverse Ag−S interactions. When such Ag12@POSS6 complex was stimulated by different solvents (acetone or tetrahydrofuran), the core Ag12 silver(I) cluster underwent reversible structural transformation between flattened cubo‐octahedral (in 1 a) and normal cubo‐octahedral (in 1 b); concomitantly shell POSS clusters rearranged from pseudo‐octahedral to quasi‐octahedral. Furthermore, the film matrix modified by 1 a or 1 b showed different hydrophobicity.