The synthesis, photophysics and reverse saturable absorption of a series of bis-cyclometalated Ir(III) complexes Ir(C∧N)2L·PF6, where L = 3,8-bis[9,9-di(2-ethylhexyl)-9H-fluoren-2-yl]-1,10-phenanthroline and C∧N = 2-phenylpyridine (ppy, 1), 2-phenylquinoline (pqu, 2), 1-phenylisoquinoline (piq, 3), 2-phenylbenzo[g]quinoline (pbq, 4), and 2,3-diphenylbenzo[g]quinoxaline (dpbq, 5), are reported. By gradually increasing the π-conjugation along the pyridine or pyrazine ring of the C∧N ligands, the energies of the lowest singlet (S1) and triplet (T1) excited states are significantly reduced, as reflected by the pronouncedly red-shifted charge transfer absorption bands at >450 nm and the emission band(s) in their UV–vis absorption and emission spectra, respectively. Additionally, our density functional theory (DFT) calculations confirm that the natures of the S1 and T1 states vary with the increased π-conjugation of the C^N ligands, with the S1 state changing from the exclusive 1LLCT (ligand-to-ligand charge tr...