Hollow CdS nanoclusters were predicted to trap alkali metals and halogen atoms inside their cavity. Furthermore, electron affinities (EA) of endohedrally halogen doped clusters and ionization potentials (IE) of endohedrally alkali doped clusters were predicted to be very similar. This makes them suitable to build cluster-assembled materials, in the same vein as do related ZnO, ZnS and MgO nanoclusters, which yield porous solid materials. With this aim in mind, we have focused on the assembly of bare Cd(i)S(i) and endohedral K@Cd(i)S(i)-X@Cd(i)S(i) (i = 12, 16, X = Cl, Br) clusters in order to obtain solids with tailored semiconducting and structural properties. Since these hollow nanoclusters possess square and hexagonal faces, three different orientations have to be considered, namely, edge-to-edge (E-E), square-to-square (S-S) and hexagon-to-hexagon (H-H). These three orientations lead to distinct zeolite-like nanoporous bulk CdS solid phases denoted as SOD, LTA and FAU. These solids are low-density crystalline nanoporous materials that might be useful in a wide range of applications ranging from molecular sieves for heterogeneous catalysis to gas storage templates.