Hierarchy in Metal–Organic Frameworks

[Image: see text] Sequence-defined nucleic acids and proteins with internal monomer sequences and arrangement are vital components in the living world, as a result of billions of years of molecular evolution. These natural hierarchical systems have inspired researchers to develop artificial hierarchical materials that can mimic similar functions such as replication, recognition, and information storage. In this Outlook, we describe the conceptual introduction of hierarchy into the design of metal–organic framework (MOF) materials. Starting with a history and background of hierarchical MOF synthesis and applications, we discuss further mesoscopic assembly strategies of MOF crystallites into hierarchical primary, secondary, tertiary, and quaternary architectures. This is followed by a highlight of the utilization of modular total synthesis for crafting MOFs with hierarchical compositions. The multiscale control over hierarchical MOF architecture formation can be rationally achieved by designing stepwise synthetic routes based on the knowledge from various fields including coordination chemistry, organic chemistry, reticular chemistry, and nanoscience. Altogether, this outlook is expected to shed light on these essential but embryonic materials and might offer inspiration for the development of the next generation of smart MOF materials with controllable heterogeneity and tailorable architectures.