The benzannulated N-heterocyclic carbene, 1,3-dibenzylbenzimidazolylidene (NHCDBZ) forms large, highly ordered domains when adsorbed on Cu(111) under ultrahigh vacuum conditions. A combination of scanning tunnelling microscopy (STM), high-resolution electron energy loss spectroscopy (HREELS), and density functional theory (DFT) calculations reveals that the overlayer consists of vertical benzannulated NHC moieties coordinating to Cu adatoms. Long-range order results from the placement of the two benzyl substituents on opposite sides of the benzimidazole moiety, with their aromatic rings approximately parallel to the surface. The organization of three surface-bound benzyl substituents from three different NHCs into a triangular array controls the formation of a highly ordered Kagome-like surface lattice. By comparison with earlier studies of NHCs on Cu(111), we show that the binding geometry and self-assembly of NHCDBZ are influenced by intermolecular and adsorbate-substrate interactions and facilitated by the flexibility of the methylene linkage between the N-heterocycle and the aromatic wingtip substituents.