In this study,the size of the titanium organic cage was controlled to achieve the restricted growth from a single Ag(Ⅰ) atom(Ag@Ti5) to rare all-carboxylate-protected superatomic Ag cluster (Ag6@Ti6).The classical octahedral Ag64+ cluster with two delocalized electrons (2e) has been encapsulated in a Ti6 organic cage,which shows high stability in air and dimethyformamide(DMF).Furthermore,larger 2e nested double-tetrahedra Ag clusters (Ag86+ and Ag87+) protected using a tetrahedral hollow metalloligand framework (Ag8@Ti4 and Ag9@Ti4) were obtained.Electrospray ionization mass spectrometry (ESI-MS) and density functional theory (DFT) calculations confirmed that there are two delocalized electrons on these small Ag clusters.This study provides a new form of protection for superatomic Ag clusters and provides a feasible strategy for the development of stable Ag clusters.