Screening experiments uncovered the key process and chemical parameters affecting the self-assembly: the ratio of the monomers, loading of acid catalyst, and the nature of the templating anion. The present study offers insight into the complex mixture of oligomeric intermediates, including their interconversion and self-organization processes en route to the macrocyclic products. HPLC-MS analysis of short oligomers revealed differences in condensation kinetics of paraformaldehyde with biotin and cyclohexyl-1,2-urea to homomeric dimers under mechanochemical agitation. The faster condensation of cyclohexyl-1,2-urea led to amplification of the homomeric cycHC [8] during aging for shortly agitated reaction mixtures. On the contrary, upon prolonged mechanochemical agitation, that ensures sufficient shuffling of monomers, higher efficiency in formation of the chimeric mixHC [8] in 37% yield was achieved. The solid-state, self-assembling approach allowed fine-tuning of the composition of the rich dynamic covalent library and directing self-assembly processes beyond statistical distribution. Diastereomeric (-)-and (+)-mixHC [8]s were isolated and their structures were characterized by DFT, NMR and SC-XRD methods. Furthermore, comparison of their affinities to chaotropic anions pointed at specific binding differences, which makes the chimeric family of HC [8] appealing for host-guest chemistry. The biotin carboxylate group of the new mixHC [8] enabled facile covalent immobilization on aminated silica. The functional material obtained was employed in the selective capture of anions, as demonstrated by the complete removal of perchlorate from an extract of a mineral model mixture. Further applications of these chiral chimeric hemicucurbiturils are currently studied.