Four metal–organic frameworks containing hexatopic connectors have been prepared and structurally characterised: [Cd3(L)(DMA)2(H2O)2] (IMP-28), [Ce2(L)(DMF)2(H2O)2] (IMP-29), [Y2(L)(DMF)2(H2O)2] (IMP-30), and [Zn2(L-H2)(4,4′-bipy)2] (IMP-31). All the MOFs have been constructed using the hybrid inorganic–organic siloxane linker hexakis(4-carboxyphenyl)disiloxane (L-H6). In each case, discrete metal-based nodes are cross-linked by the octahedrally disposed connector to afford 3D polymeric structures. The underlying nets in these MOFs have been evaluated through deconstruction of their crystal structures and subsequent topological analysis. Examples of MOFs built from hexatopic linkers, and especially those with octahedral predispositions such as in L, remain scarce and the topologies ascribed to some of these MOFs are unique.