A judicious selection of substituents in cyclometalating 2-arylbenzimidazoles and an ancillary aromatic 1,3-diketone enabled the creation of heteroleptic iridium(III) complexes demonstrating strong light absorption up to 500 nm (ε ≈ 10 000-12 000 M-1 cm-1). The complexes, which were studied by various spectroscopic techniques, single-crystal X-ray diffraction and cyclic voltammetry, displayed tunable absorption maxima depending on the nature of substituents and their positions. The experimental study was corroborated by quantum chemical calculations, which showed an increased contribution of intraligand charge transfer transitions to the visible light absorption in the case of complexes containing electron-withdrawing substituents in the ligands. Despite being of high intensity, some of these transitions are responsible for the formation of the excited states located at large distances from the 'anchoring' fragment incorporated in the ancillary ligand. In turn, incorporation of electron-donating substituents at the para-position to the Ir-C bonds increases the number of excited states located on the ancillary ligand. The destabilization of the HOMO, which is caused by the increase in the electron-donating ability of the substituents in the metalated rings, translated into negative shifts of the Ir4+/Ir3+ redox potential, affecting, in some cases, the degree of electrochemical reversibility of the complexes. Several complexes having strong light-harvesting characteristics and undergoing reversible oxidation in the appropriate potential range were used for coating the TiO2 photoanodes, which reached an efficiency of 2.15% upon irradiation with the standard AM 1.5 spectrum.