The self-assembly of the perchlorinated hexa-peri-hexabenzocoronene (PCHBC) molecules on Au(111) has been studied by a low temperature scanning tunneling microscopy (STM) combining with density functional theory based first principle calculations. Highly ordered supramolecular networks with single domains limited by the terraces are formed on Au(111) substrate. High resolution images of the PCHBC molecules, confirmed by first principle simulations, are obtained. It reveals the close-packed arrangement of the PCHBC molecules on Au(111). The calculated charge distribution of PCHBC molecules shows the existence of attractive halogen-halogen interaction between neighboring molecules. Compared with the disordered adsorption of hexa-peri-hexabenzocoronene on Au(111), we conclude that the formation of attractive Cl∙∙∙Cl interactions between neighbors is the key factor to form the highly ordered, close-packed networks. Due to the steric hindrance resulted from the peripheral chlorine atoms, the PCHBC molecule is contorted and forms the doubly concave conformation, which is different from the hexa-peri-hexabenzocoronene with a planar structure. By using this supramolecular network as a template, we deposited C60 molecules on it at room temperature with low coverage. The STM images taken at low temperature show that the C60 molecules are mono-dispersed on the networks and adsorb on top of the PCHBC molecules, forming a typical concave-convex host-guest system.