<p>Open-framework materials are constructed by connecting molecular components via strong bonds. It is generally believed that non-covalent interactions are too weak to hold the building blocks and generate stable open voids. Here we show that van der Waals interactions enable the construction of robust three-dimensional frameworks, referred to as van der Waals open frameworks (WaaFs). The key to successful synthesis of WaaFs is the use of octahedral metal–organic polyhedra with size larger than 2 nm as building blocks and their packing into a sparse diamond network with large extrinsic porosity. The well-defined faces composed of multiple planar moieties increase the intermolecular contact area to achieve an interaction energy above 400 kJ mol⁻¹. We show that the WaaFs exhibit high thermal stability and high specific surface area as well as framework assembly with a reversible nature.</p><p></p>