Nature Chemistry, Published online: 12 August 2026; doi:10.1038/s41557-026-02223-5 Conductive van der Waals metal–organic frameworks (vdW–MOFs) are an emerging class of electronic materials whose properties are highly sensitive to layer stacking. Now, a strategy enables precise control over the stacking structures of vdW–MOFs by using solvents to direct the formation of metastable supramolecular ligand aggregates prior to framework assembly.