Abstract: | Building framework materials with desirable properties and enhanced functionalities with nanocluster/superatom complexes as building blocks remains a challenge in the field of nanomaterials. In this study, the chiral Au1Ag22(S‐Adm)12]3+ nanocluster/superatom complex (SC, in which S‐Adm=1‐adamantanethiol) was employed as a building block to construct the three‐dimensional (3D) superatom complex inorganic framework (SCIF) materials SCIF‐1 and SCIF‐2 through inorganic SbF6? linkers. SCIF‐1 is racemic due to the assembly of two SC enantiomers in a single crystal. In SCIF‐2, the SC enantiomers are packed in separate crystals, thus producing larger channels and a circularly polarized luminescence (CPL) response. These two 3D SCIF materials exhibit unique sensitive photoluminescence (PL) in protic solvents. Our study provides a new pathway for creating novel open‐framework materials with superatom complexes and a foundation for the further development of 3D framework materials for sensing and other applications. |