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An improved understanding of preferential solute transport in soil macropores would enable more reliable predictions of the fate of agrochemicals and the protection of water quality in agricultural landscapes. The objective of this study was to investigate how soil organic carbon (SOC) and soil texture shape soil pore structure and thereby determine the susceptibility to preferential transport under steady-state near-saturated flow conditions. To do so, we took intact topsoil samples from an arable field that has large variations in SOC content (1.1–2.7%) and clay content (8–42%). Soil pore structure was quantified by X-ray tomography and soil water retention measurements. Non-reactive solute transport experiments under steady-state near-saturated conditions were carried out at irrigation rates of 2 and 5 mm h−1 to quantify the degree of preferential transport. Near-saturated hydraulic conductivities at pressure heads of −1.3 and −6 cm were also measured using a tension disc infiltrometer. The results showed that larger abundances of small macropores (240–720 µm diameter) and mesopores (5–100 µm diameter) resulted in weaker preferential transport, due to larger hydraulic conductivities in the soil matrix that prevented the activation of water flow and solute transport in large macropores. In particular, the degree of preferential transport was most strongly and negatively correlated with the mesoporosity in the 30–100 µm diameter class. In contrast, the degree of preferential transport was not correlated with connectivity measures (e.g. the percolating fraction and critical pore diameter for the macropore network), probably because i.) the pore space of almost all samples was highly connected, being dominated by one percolating cluster, and ii.) only a part of this percolating macroporosity was active under the near-saturated conditions of the experiment. We also found that the degree of preferential transport was strongly and negatively correlated with clay content, whilst the effects of SOC were not significant. Nevertheless, macroporosity in the 240–720 µm diameter class and mesoporosity were positively correlated with SOC content in our soils and in some previous studies. Therefore, SOC sequestration in arable soils may potentially reduce the risk of preferential transport under near-saturated flow conditions through better developed networks of small macropores and mesopores.