The first C∧C∧Ncyclometalatedcomplexes of iridium that bear tridentate pyridylbiphenylene ligands are reported herein. These complexes were synthesized in good yields by means of the directed C–C bond activation of biphenylene with the assistance of pyridyl group precoordination. Their photoluminescent performances were also studied and show uniqueluminescentproperties at longer wavelengths in