Platinum (Pt)-tipped electrodes are frequently employed to measure the soil redox potential (E H ). Thereby, the timely transition from reducing towards oxidising soil conditions is one of the most important biogeochemical changes that can occur in soil. This condition is mainly linked to the air-filled pore volume (ε) and pore geometries. However, even when the Pt electrodes are located in close vicinity to each other, E H readings behave non-uniformly, presumably due to the millimetre scaled heterogeneity of pore spaces controlling oxygen (O 2 ) availability and transport. In this study, we examined the ε distribution and pore connectivity in the close vicinity of a Pt electrode during an artificial evaporation experiment using an undisturbed soil sample (Ah-horizon, Calcaric Gleysol). We combined physio-chemical methods with non-destructive X-ray computed microtomography (μCT) and 3D-image analysis. μCT scans were conducted at three-time points, that is, reducing conditions with E H < À100 mV (CT-1), the transition from reducing towards oxidising conditions with an E H increase > 5 mV h À1 (CT-2), and oxidising conditions with E H > 300 mV (CT-3). We observed that the shift from reducing towards oxidising conditions took place at an air-filled porosity (ε CT ) of ~0.03 cm 3 cm À3 , which matches very with gravimetrically calculated data obtained by tensiometry of ε ~0.05 cm 3 cm À3 . Besides the relation of E H and ε, image analysis revealed that a connected ε CT (ε CT_conn ) of ~0.02 cm 3 cm À3 is needed to enable enhanced O 2 diffusion from the soil surface towards the Pt surface and facilitate a straightforward E H response. We conclude that ε CT_conn is a critical parameter to assess aeration processes in temporarily water-saturated soils to characterise a switch in redox conditions.Kristof Dorau and Daniel Uteau contributed equally to this study.