On-surface synthesis with molecular precursors has emerged as the de facto route to atomically well-defined graphene nanoribbons (GNRs) with controlled zigzag and armchair edges. On Au(111) and Ag(111) surfaces, the prototypical precursor 10,10′-dibromo-9,9′-bianthryl (DBBA) polymerizes through an Ullmann reaction to form straight GNRs with armchair edges. However, on Cu(111), irrespective of the bianthryl precursor (dibromo-, dichloro-, or halogen-free bianthryl), the Ullmann route is inactive, and instead, identical chiral GNRs are formed. Using atomically resolved noncontact atomic force microscopy (nc-AFM), we studied the growth mechanism in detail. In contrast to the nonplanar BA-derived precursors, planar dibromoperylene (DBP) molecules do form armchair GNRs by Ullmann coupling on Cu(111), as they do on Au(111). These results highlight the role of the substrate, precursor shape, and molecule–molecule interactions as decisive factors in determining the reaction pathway. Our findings establish a new d...