“…The macroscopic supramolecular assembly (MSA) refers to a self-assembly of micrometer-to-millimeter building blocks based on multivalent non-covalent interactions − and has developed rapidly toward the goal of “self-assembly at all scales” by bridging the molecular assembly behaviors to the macroscopic materials. Owing to the characteristics of interfacial interactions between micrometer-to-millimeter surfaces, studies of the MSA mechanism are used to understand diverse non-covalent interfacial phenomena such as bio-/wet adhesion, , self-healing. − Meanwhile, MSA has been developed as a facile modular fabrication strategy to prepare heterogeneous structures, bio-scaffolds, , actuators, and information storage materials. − To extend the applicable scenarios of MSA, much progress has been achieved on enriching supramolecular interactions (molecular recognition, , hydrogen bonding, electrostatic interactions, DNA hybridization, , and so on), extending building block materials (gels, ,,− , elastomers, ,, quartz, and metal) that could realize MSA, and revealing the assembly mechanism. ,,, These studies have demonstrated that MSA is not simply an amplification of the building block size from the molecular self-assembly but requires additional factors (e.g., external energy and fast interfacial adhesion) to facilitate the binding of two macroscopic surfaces. In a typical MSA process, micrometer-to-millimeter building blocks are placed in water and extra shaking or rotation is necessary to trigger the interactions, during which the collision frequency is much lower than that of molecular thermal motions.…”