Hexaphenylbenzene (HPB) derivatives, HPB-6a and HPB-6pa, can form a supramolecular network which is stabilized by the intermolecular hydrogen bonding between carboxyl group at an octanoic acid/graphite interface. The observation of the heterogeneous bilayer structure formed exclusively by coronene and HPB-6pa at the octanoic acid/graphite interface is reported. Pronounced selectivity of coronene for the supramolecular networks with different sizes is reflected through the formation of bilayer structure for HPB-6pa network with the introduction of coronene as the guest species, indicating stronger interactions between HPB-6pa and coronene.