In summary, the solvent-free synthesis offers a platform with high versatility and applicability, which allows the preparation of multivariate ZIFs, enabling the incorporation of bulkier ligands retaining the sodalite topology. We have demonstrated the versatility of this approach with three different binary combinations of ligands and three different metal centres, resulting in eight novel ZIFs with different response towards N2 sorption. In this sense, recent studies have shown the importance of the metal centres in lowering the pressure at which the gate opening occurs in ZIF-8, but we demonstrate that the use of mixed-ligand frameworks is an alternative approach to modify the physical properties of ZIFs. Theoretical calculations confirm the preference of a SOD topology when using mixture of ligands, which is rationalized by invoking interligand steric hindrance effects. This solvent-free approach allows to design multivariate ZIFs with network complexity, thus opening the door to also combine different metals in the same framework, and paving the way to reach similar complexity in ZIFs as that observed in other promising MOFs.