The composition of protection monolayer exerts great influence on the molecular and electronic structures of atomically precise monolayer protected metal nanoclusters. Four isostructural Ag/cyanurate/phosphine metallamacrocyclic monolayer protected Ag22 nanoclusters are synthesized by kinetically controlled in‐situ ligand formation‐driven strategy. These eight‐electron superatomic silver nanoclusters feature an unprecedented interfacial bonding structure with diverse E‐Ag (E=O/N/P/Ag) interactions between the Ag13 core and metallamacrocyclic monolayer, and displays thermally activated delayed fluorescence (TADF), benefiting from their distinct donor‐acceptor type electronic structures. This work not only unmasks a new core‐shell interface involving cyanurate ligand but also underlines the significance of high‐electron‐affinity N‐heterocyclic ligand in synthesizing TADF metal nanoclusters. This is the first mixed valence Ag0/I nanocluster with TADF characteristic.