Here, the structural transformations of H₄ETTC induced by coronene (COR) and selective adsorption behaviors of COR in different templates were investigated by scanning tunnelling microscope (STM). It was discovered that the assembled architecture of H₄ETTC at the HOPG/ heptanoic acid interface depended on the concentration of COR, and the clusters of COR were obtained in the kagomé nanoporous network of H₄ETTC molecules at a high concentration of COR solution. In addition, COR clusters can also be formed in the hexagonal porous structure of hexaphenylbenzene (HPB) molecules modified by alkyl chains at the HOPG/heptanoic acid interface. When both H₄ETTC and HPB assembly structures, based on hydrogen bonding and van der Waals force respectively, were selected as the host templates, COR showed selectivity for HPB template to form HPB/COR hexagonal host–guest architecture. Density functional theory (DFT) calculations were also performed to disclose the mechanisms involved.