Photoactive Iridium(III) complexes are a popular synthetic tool. The impact of ligand design on their photoredox properties has been widely studied, but similar approaches to develop more potent photosensitizers are still absent. We report herein the preparation, characterization and catalytic application of a new family of Iridium(III) complexes that proved superior to their widely-used commercial peers. The best results were observed when naphthyl pendants were installed to the ligands, which could stabilize the triplet intermediates involved in energy-transfer reactions via radical-p dispersion interactions.