Two metal-organic frameworks (MOFs) based on metal-organic cuboctahedra were prepared using a rigid C3 symmetric ligand, where Zn polyhedron-based MOF (PMOF-2(Zn)) did not show any significant gas sorption behavior, whereas the isostructural Cu polyhedron-based MOF (PMOF-2(Cu)) showed a large surface area of approximately 4180 m2 g(-1), high hydrothermal stability, and very promising H2 sorption properties.