Oxygen (O2) availability in soils is vital for plant growth and productivity. The transport and consumption of O2 in the root zone is closely linked to soil moisture content, the spatial distribution of roots, as well as structure and heterogeneity of the surrounding soil. In this study, we measure three‐dimensional root system architecture and the spatiotemporal dynamics of soil moisture (θ) and O2 concentrations in the root zone of maize (Zea mays) via non‐invasive imaging, and then construct and parameterize a reactive transport model based on the experimental data. The combination of three non‐invasive imaging methods allowed for a direct comparison of simulation results with observations at high spatial and temporal resolution. In three different modeling scenarios, we investigated how the results obtained for different levels of conceptual complexity in the model were able to match measured θ and O2 concentration patterns. We found that the modeling scenario that considers heterogeneous soil structure and spatial variability of hydraulic parameters (permeability, porosity, and van Genuchten α and n), better reproduced the measured θ and O2 patterns relative to a simple model with a homogenous soil domain. The results from our combined imaging and modeling analysis reveal that experimental O2 and water dynamics can be reproduced quantitatively in a reactive transport model, and that O2 and water dynamics are best characterized when conditions unique to the specific system beyond the distribution of roots, such as soil structure and its effect on water saturation and macroscopic gas transport pathways, are considered.