A 3D polycage network, denoted as [Zn8L4I8], was generated by employing enantiopure pyridyl-functionalized metallosalalen units with Zn II iodide. This network was interconnected by pentahedral cages, which were created by neighboring pentamers. The amphiphilic helical cavity, adorned with chiral NH functionalities, can selectively interact with enantiomeric saccharides in solution, exhibiting enantioselectivity factors ranging from 2.480-4.943. In the solid state, it also demonstrates enantioselective fluorescence enhancement ratios of 1.30 to 3.60 when interacting with five enantiomeric amines.