The spontaneous organization of molecular species relies on non-covalent interactions, resulting in intricate aggregates. Such supramolecular self-assembly can facilitate the formation of covalent bonds leading to complex molecules, and may be exceptionally responsive to minor changes in the external stimuli, resulting in the amplification of particular products. Under conditions of increased molecular crowding, the dynamics of interaction between species is accelerated compared to a dilute environment, which has been demonstrated for strongly hydrogen-bonded base pairs of nucleic acids. Furthermore, at extreme concentrations in the solid state, where non-covalent interactions are stronger, the formation of products that are less favorable in solution can occur. Mechanochemical activation enhances chemical reactivity and provides a solvent-free sustainable approach in chemical syntheses. Single-bridged cucurbituril-type molecular containers, hemicucurbit[n]urils (HC[n]s) are renowned for their anion-binding properties and are typically assembled from urea monomers in a one-pot reaction with dynamic covalent chemistry (DCC). Although the size of the macrocycle can be controlled by anion templation, HCs prevalently consist of six units. Up to date, 8-membered HCs have been synthesized exclusively from chiral C 2 -symmetric cyclohexa-1,2-diylurea (CU) monomers, and the corresponding (R,R)-and (S,S)-cyclohexanohemicucurbit [8]urils (cycHC [8]) can be assembled both in solution and the solid state . Their larger cavity expands the range of applications, and insertion of another functional monomer, such as D-biotin, into cycHC [8] scaffold can further enhance receptor versatility. Biotin is a naturally occurring and commercially available compound with a carboxylic group suitable for derivatization. Furthermore it has previously been used in the synthesis of chiral macrocycles . So far, the reported chimeric HCs assembled from non-equivalent urea monomers have been limited to six-membered hybrid HCs prepared in solution via multi-step approaches, and mono-functionalized bambus [6]urils obtained in a one-pot reaction. The difficulties in the single-step formation of non-uniform oligomeric macrocycles arise from a plethora of possible linear and cyclic intermediates. Consequently, arranging a chaotic mixture into a well-organized molecule presents considerable challenges, and the number of combinations increases with the number of monomeric units.