The timing and magnitude of greenhouse gas (GHG) production depend strongly on soil oxygen (O2) availability, and the soil pore geometry characteristics largely regulate O2 and moisture conditions relating to GHG biochemical processes. However, the interactions between O2 dynamics and the concentration and flux of GHGs during the soil moisture transitions under various soil pore conditions have not yet been clarified. In this study, a soil-column experiment was conducted under wetting–drying phases using three pore-structure treatments, FINE, MEDIUM, and COARSE, with 0 %, 30 %, and 50 % coarse quartz sand applied to soil, respectively. The concentrations of soil gases (O2, nitrous oxide (N2O), carbon dioxide (CO2), and methane (CH4)) were monitored at a depth of 15 cm hourly, and their surface fluxes were measured daily. Soil porosity, pore size distribution, and pore connectivity were quantified using X-ray computed microtomography. The soil O2 concentrations were found to decline sharply as soil moisture increased to the water holding capacities of 0.46, 0.41, and 0.32 cm cm−3 in the FINE, MEDIUM, and COARSE, respectively. The dynamic patterns of the O2 concentrations varied across the soil pore structures, decreasing to anaerobic in FINE (<0.01 %) and MEDIUM (0.02 %), and to hypoxic (4.42 %) in COARSE. Correspondingly, the soil N2O concentration was the highest in FINE (101 μL L−1) and the lowest in COARSE (10 μL L−1), whereas the highest surface N2O flux was observed in MEDIUM (131 μg N m−2 h−1). As soil CO2 concentrations declined, CO2 fluxes increased from FINE to MEDIUM to COARSE. Most pores of FINE, MEDIUM, and COARSE were 15–80 μm, 85–100 μm, and 105–125 μm, respectively, in terms of diameter. The X-ray CT visible (>15 μm) porosity in FINE, MEDIUM and COARSE were 0.09, 0.17, and 0.28 mm3 mm−3, respectively. The corresponding Euler-Poincaré numbers were 180,280, 76,705, and −10,604, respectively, indicating higher connectivity in COARSE than in MEDIUM or FINE. In soil dominated by small air-filled porosity which limits gas diffusion and result in low soil O2 concentration, N2O concentration was increased and CO2 flux was inhibited as the moisture content increased. The turning point in the sharp decrease in O2 concentration was found to correspond with a moisture content, and a pore diameter of 95–110 μm was associated with the critical turning point between holding water and O2 depletion in soil. These findings suggest that O2-regulated biochemical processes are key to the production and flux of GHGs, which in turn are dependent on the soil pore structure and a coupling relationship between N2O and CO2. Improved understanding of the intense effect of soil physical properties provided an empirical foundation for the future development of mechanistic prediction models for how pore-space scale processes with high temporal (hourly) resolution up to GHGs fluxes at larger spatial and temporal scales.