AbstractIridium‐catalyzed borylations of aromatic C−H bonds are highly attractive transformations because of the diversification possibilities offered by the resulting boronates. These transformations are best carried out using bidentate bipyridine or phenanthroline ligands, and tend to be governed by steric factors, therefore resulting in the competitive functionalization of meta and/or para positions. We have now discovered that a subtle change in the bipyridine ligand, namely, the introduction of a CF₃ substituent at position 5, enables a complete change of regioselectivity in the borylation of aromatic amides, allowing the synthesis of a wide variety of ortho‐borylated derivatives. Importantly, thorough computational studies suggest that the exquisite regio‐ and chemoselectivity stems from unusual outer‐sphere interactions between the amide group of the substrate and the CF₃‐substituted aryl ring of the bipyridine ligand.