Template-directed polymerization is an effective approach used to afford regular 2D covalent organic frameworks (COFs), thus the regularity of the template is crucial for the quality of the resulting 2D COFs. For the Ullmann reactions on Cu(111), aryl iodides and bromides are activated at low temperature to form organometallic C–Cu–C structures, which lead to kinetic trapping and irregular organometallic networks. Therefore, the subsequent annealing step can only afford irregular 2D COFs. In this manuscript, the molecule 4,4′′-dibromo-5′-(4-chlorophenyl)-1,1′:3′,1′′-terphenyl incorporated two Br terminals and one Cl terminal has been used to demonstrate different reactivities of a C–Cl bond and a C–Br bond via the hierarchical activation of the C–Br bond and the C–Cl bond on Cu(111). At room temperature, zigzag, armchair, and ring-like organometallic chains formed due to the activation of the C–Br bond to generate a C–Cu–C structure while C–Cl remained intact, illustrating that the C–Cl bond is more stable than C–Br. Further annealing at 433 K activated the C–Cl bond to produce regular organometallic networks as the thermodynamic product. Using the simpler molecule 1,3,5-tris(4-chlorophenyl)benzene as the precursor, the self-assembly of the intact molecules was observed on Cu(111) at 300 K without activation of the C–Cl bond. After annealing at 433 K, similar thermodynamically stable organometallic networks formed directly, which were used as a template to generate regular 2D COFs upon further annealing at 510 K.