The photo-excitation and relaxation of a new cyclometalated complex, Ir(ppy)2fppy, is investigated through the measurement of absorption and photoluminescence spectra. Comparison of Ir(ppy)2fppy with Ir(ppy)3 reveals that the lowest energy excited state of Ir(ppy)2fppy is localised on the aldehyde-substituted ligand, thus giving the complex its characteristic orange emission (λmax ≈ 600 nm). OLEDs containing Ir(ppy)2fppy doped into poly(vinylcarbazole) (PVK) exhibit the same characteristic emission as found in solution, implying efficient energy transfer between the PVK and the iridium complex. Our results provide the potential for the synthesis of iridium complexes with different emission wavelengths through the modification of only one ligand.