On-surface Ullmann coupling has been intensely utilized for the tailor-made fabrication of conjugated frameworks towards molecular electronics,however,reaction mechanisms are still limitedly understood.Herein,we provide a comprehensive elucidation of the surface Ullmann coupling of 2,7-dibromopyrene (Br2Py) on Ag(111) by scanning tunnelling microscopy (STM),X-ray photoelectron spectroscopy (XPS) and density function theory (DFT),and reveal that the Ullmann reaction path is unique regardless of predesigned assembled structures.By manipulating deposition conditions,diverse assembled architectures have been constructed for Br2Py on Ag(111),including the ladder phase,parallel arrangement,hexagonal patterns from monomers or Kagome lattices based on organometallic (OM) dimers.Intriguingly,stepwise annealing leads to an identical reaction diagram for the surface Ullmann coupling from individual assembled structures convergent into the brick-wall-pattern OM dimers first,which is deemed to be a stable phase,and then into elongated OM chains in order and eventually long-range polymers with direct C--C coupling.While the reaction mechanism is demonstrated to be dominated by the metal coordinated and halogen bonding motifs,interestingly,it has also been revealed that surface adatoms and dissociated Br atoms play a crucial role in coupling reactions.In contrast to previous reports demonstrating the manipulation of Ullmann reactions by preassembled strategy,herein,weak intermolecular interaction in assembled nanostructures is immediately suppressed by strong covalent bonding during reactions.Importantly,our report proposes essential insights on fundamental understanding of surface Ullmann coupling towards high-yield surface synthesis.