Long intervals of single geomagnetic polarity (superchrons) reflect geodynamo processes, driven by core–mantle boundary interactions; however, it is not clear what initiates the start and end of superchrons, other than superchrons probably reflect lower heat flow across the core–mantle boundary compared with adjacent intervals. Here geomagnetic polarity timescales, with confidence intervals, are constructed before and following the reverse polarity Kiaman (Carboniferous–Permian) and Moyero (Ordovician) superchrons, providing a window into the geodynamo processes. Similar to the Cretaceous, asymmetry in reversal rates is seen in the Palaeozoic superchrons, but the higher reversal rates imply higher heatflow thresholds for entering the superchron state. Similar to the Cretaceous superchron, unusually long-duration chrons characterize the ∼10 Myr interval adjacent to the superchrons, indicating a transitional reversing state to the superchrons. This may relate to a weak pattern in the clustering of chron durations superimposed on the dominant random arrangement of chron durations.