Palladium-catalysed direct 5-arylation of metallated thiophenes of fac-Ir(N^C(3')-thpy)(3) with aryl bromides via C-H bond functionalisation allows the synthesis of a variety of new Ir complexes in only one step (thpyH = 2,2'-thienylpyridine). The method offers simple modification of the nature of the ligand and hence of the photophysical properties of such complexes.