This review highlights the state-of-the-art progress achieved in two-dimensional covalent organic frameworks (COFs) with hierarchical porosity, an emerging class of COFs constructed by integrating different types of pores into one framework.

New linkage chemistry will endow covalent organic frameworks (COFs) with not only structural diversity but also fascinating properties. However, to develop a new type of linkages has been a great challenge. We herein report the first two COFs using aminal as the linkages. These two COFs have been synthesized by condensation of secondary amine and aldehyde. They crystallize in cpi net, which is a new topology for COFs. The aminal linkage is found to favor reservation of photophysical property of the monomers due to its tetrahedral geometry and nonconjugated feature. These aminal-COFs exhibit good thermal stability and high chemical stability under neutral and basic conditions.