The formation of additional phenyl rings on surfaces is of particular interest because it allows for the building-up of surface covalent organic frameworks. In this work, we show for the first time that the cyclotrimerization of acetyls to aromatics provides a promising approach to 2D conjugated covalent networks on surfaces under ultrahigh vacuum. With the aid of scanning tunneling microscopy, we have systematically studied the reaction pathways and the products. With the combination of density functional theory calculations and X-ray photoemission spectroscopy, the surface-assisted reaction mechanism, which is different from that in solution, was explored.