Long-term irrigation promotes the infiltration of water in the thick, stratified loess layer, significantly raising the groundwater table and triggering a series of landslides in loess platform areas. The soil–water characteristic curve (SWCC) of loess buried at different depths affects the unsaturated infiltration process and is intricately connected to the soil’s microstructure. The SWCCs, scanning electron microscope (SEMs), and pore size distributions (PSDs) for five sets of undisturbed loess samples at depths ranging from 3.4 to 51.9 m are shown in this paper. The results indicate that the fitting parameter air entry value (AEV) of the SWCC rises from 13.67 kPa to 40.19 kPa as the depth increases from 3.4 to 51.9 m. And the saturated volumetric water content drops by 10.9%, with a notable SWCC shape difference between the transition and residual zones observed. Additionally, the total porosity of undisturbed loess falls by 12% when the depth increases from 3.4 to 51.9 m, while the macropores and mesopores reduce by 3.6% and 12.1%, respectively. These findings highlight the control of the pore structure on the SWCC and emphasize the correspondence between the SWCC and PSD. The conclusions also illustrate that the compaction effect changes the microstructure characteristics of loess, thereby affecting the soil’s water retention behavior.