Charcoal samples from ancient human occupation sites in Australia have been subjected to a rigorous pretreatment and stepped combustion regime in order to explore the possibility that these sites may be older than previous radiocarbon dating had suggested. In one case, the Devil’s Lair site in southwest Australia, the methodology has clearly removed vestiges of contamination by more modern carbon and has led to a revised radiocarbon chronology that provides evidence for human occupation of southwest Australia by at least 44 ka BP and probably by 46–47 ka BP. In contrast, charcoal from the Nauwalabila site has been so severely altered that insufficient of the original carbon remains for reliable 14C dating. Finally, where the charcoal is well preserved, such as at the Carpenter’s Gap site, the new results provide reassurance that earlier 14C results of ~40 ka BP are indeed true ages and are not simply at the limit of the 14C technique.