Surface-based synthesis is a promising approach for the creation of complex molecular nanostructures, including macrocycles. However, despite recent advances in underground macrocycling, selective synthesis of monodisperse and multi-component macrocycles remains a challenge. Here, we provide information on surface formation [6 + 6] Schiff – Base macrocycles with the help of Dynamic Covalent Chemistry. Microcycles form two-dimensional crystalline domains across micrometers, which dynamically convert open-chain oligomers into well-defined ∼ 3.0 nm hexagonal macrocycles. We also hypothesize that by adjusting the length of the alkyl substituents, it is possible to control which of the three possible products – oligomers, macrocycles or polymers form on the surface. on the place Density tunneling microscope imaging, together with density functional theory calculations and molecular dynamics simulation, identifies the synergistic effect of the surface framework and the solvent, leading to the advantage of surface macrocyclization.