macrocycles. They have been also employed to modify the surface properties of metal nanoparticles via noncovalent host−guest interactions, [31] covering their applications in drug delivery, [32] highly sensitive sensors, [33] selective catalysis, [34] and so on.In addition to their intensive applications based on their host−guest chemistry, macrocycles have also been used as building blocks to construct solid materials including porous organic polymers (POPs), [35,36] metal-organic frameworks (MOFs), [37][38][39][40][41][42][43] and crystalline organic materials (COMs). [44][45][46][47][48][49][50][51][52][53][54][55][56][57] Particular attention should be paid to COMs, a class of organic materials featuring facile preparation, high crystallinity, structural diversity, chemical stability, solution-processability, etc. [58][59][60][61][62][63][64][65][66][67][68][69][70] Different from MOFs that are composed of both inorganic (metal ions) and organic species (organic ligands) through coordination, COMs refer to a kind of crystalline materials composed of pure organics connected by either covalent or noncovalent bonds. [71][72][73] For COMs connected by noncovalent bonds, the typical materials are organic molecular crystals with intriguing properties such as semiconductor, [53] porosity, [68] etc. Owing to the inefficient packing of organic building blocks in the crystal state, some molecular crystals display extrinsic porosity, which are often termed as hydrogen-bonded organic frameworks (HOFs) [74,75] or supramolecular organic frameworks (SOFs). [76][77][78][79][80] For COMs connected by covalent bonds, typical materials are crystalline covalent organic frameworks (COFs), which were firstly reported in 2005 by Yaghi and co-workers [44] Benefitting from rigid chemical bonds and building blocks, COFs show permanent and well-ordered porosity. [45][46][47][48] Supramolecular-macrocycle-based COMs, a class of COMs with macrocycles as the main building blocks, have drawn particular attention in recent years. According to their components, supramolecular-macrocycle-based COMs can be classified into two main categories, the ones composed of pure macrocycles and the others consisting of macrocycles and other simple organic building blocks. Owing to their prefabricated cavities of a certain type, some of macrocycle-based COMs exhibit intrinsic microporosity for guest adsorption in the solid state. On the other hand, the extrinsic porosity of some macrocyclebased COMs may form due to the inefficient packing of these rigid macrocyclic molecules in the crystalline state. In certain circumstances, both intrinsic and extrinsic microporosity can be created in a single lattice of a certain COM, thus leading to Supramolecular macrocycles are well known as guest receptors in supramolecular chemistry, especially host−guest chemistry. In addition to their wide applications in host−guest chemistry and related areas, macrocycles have also been employed to construct crystalline organic materials (COMs) owing to their particular structur...