Precise determinations of the rates and durations of Palaeozoic biogeochemical events are largely unavailable. Here, we present two new high-precision U–Pb (zircon) dates from volcanic ash deposits from the Ludlow Series (Silurian System) of Podolia, Ukraine, that yielded weighted mean 206Pb/238U dates of 424.08 ± 0.20 (0.29) [0.53] Ma and 422.91 ± 0.07 (0.21) [0.49] Ma (analytical, tracer and total uncertainties). These new dates bracket the largest post-Cambrian global carbon cycle perturbation (Lau Excursion) and constrain the ‘Ludlow Rise’ in 87Sr/86Sr. These chronostratigraphically well-controlled dates improve the calibration of the Silurian time scale and provide the first determinations of the rates of biogeochemical change during the Ludlow Epoch.