The reaction of a K4[{Re6Si8}(OH)a6]·8H2O rhenium cluster salt with 4,4′‐bipyridine (bpy) or 4‐aminopyridine (apy) in an aqueous solution at mild temperature and pressure conditions lead to cluster functionalization and to the formation of two new compounds [{Re6Si8}(OH)a2(bpy)a4]·bpy·4H2O (1) and [{Re6Si8}(OH)a2(apy)a4]·2apy·2H2O (2). Their crystal structures are built up from trans‐[{Re6Si8}(OH)a2(L)a4] neutral units and the cohesions of both supramolecular frameworks are based on π–π stacking as well as hydrogen bonds, involving the cluster units trans‐[{Re6Si8}(OH)a2(L)a4], interstitial L ligands and water molecules. 1 and 2 present 2D and 3D cluster frameworks, respectively. Both compounds show red‐NIR luminescence in the solid states. DFT calculations demonstrate that association of face capped Re6 clusters with bpy and apy ligands enabled to form supramolecular frameworks that retain luminescent properties of the cluster units.