The long and complex Archaean evolution of the Napier Complex of Enderby Land, characterized by high-grade metamorphism and several strong deformations, is reassessed in the light of new SHRIMPU–Pb zircon dating results bearing on the ages of protoliths and possible regional extents of distinct Archaean tectonothermal events. Initial felsic igneous activity occurred over a significant time interval c. 3800 Ma ago. An age of 2980±9 Ma for the emplacement of charnockite at Proclamation Island might date the oldest tectonothermal event to be recognized in the Napier Complex. An ensuing, very-high grade, previously imprecisely dated tectonothermal event occurred at 2837±15 Ma. U–Pb zircon ages ranging from 2456+8/−5 Ma to 2481±4 Ma date a subsequent, protracted high-grade tectonothermal event. Whereas the ~2840 Ma event is of regional importance in the Amundsen Bay-Casey Bay area, it is possible that the ~2980 Ma event was of only moderate grade, minor importance, or even absent, in that part of the Complex. If so, the apparent trend to very-high temperature metamorphism in the Tula and Scott mountains compared with the Napier Mountains may reflect two distinct metamorphic events rather than a simple baric and thermal gradient. The oldest crustal component in the Napier Complex appears to have been of igneous derivation. Zircon populations in paragneisses at Mount Sones are similar to those in the nearby orthogneisses, which therefore may have been basement. Another paragneiss, in the Casey Bay area, yields no zircons older than 2840 Ma, probably indicating that pre-3000 Ma crust, which is now located nearby, was not exposed at the time of sedimentation there. The isotopic data are quite complex, particularly in rocks that experienced postcrystallization metamorphic temperatures of 1000°C or more. It is postulated that this complexity, which was largely the product of migration of radiogenic Pb within the zircon grains in ancient times, and produced local excesses of this element with respect to its parent U, was caused by volume diffusion at these abnormally high regional crustal temperatures.