We report the synthesis and characterization of ten neutral bisheteroleptic iridium(III) complexes with 2-phenylbenzimidazole cyclometallating ligand and picolinate as ancillary ligand. The 2-phenylbenzimidazole has been modified by selected substituents introduced on the cyclometallating ring and/or on the benzimidazole moiety. The integrity of the complexes has been assessed by NMR spectroscopy, by high-resolution mass spectrometry and by elemental analysis. The complexes are demonstrated to be highly phosphorescent at room temperature and a luminescence study with comprehensive ab initio calculations allow us to determine the lowest emitting excited state which depends on the substituent nature and its position on the cyclometallating ligand.