Soil structure is one of the major factors to affect soil salinization in high evaporation areas. Revealing the effects of desulfurization steel slag (DSS) on the pore structures in saline-sodic soil is critical for evaluating the remediation effects and understanding the mechanisms of various soil processes involved. In this study, the multiscale pore structure in DSS-amended soil was quantified by multiscale X-ray tomography. Soil macroaggregates (>5 mm in diameter) and intact soil cores (5 × 20 cm in size) were collected from a field experiment of DSS reclamation for 1 yr (T1) and 4 yr (T4), respectively. The saline-sodic soil without DSS treatments was taken as the control (CK). For soil aggregates, the difference in total porosity between T1 and T4 treatments is insignificant. For soil cores, the total porosity of the T4 treatment significantly decreased compared with the T1 treatment. The compact and homogeneous pore structures of CK benefits the ascension of the capillary water, which directly related to soil salinization. However, the alteration of pore structure in DSS-amended soils posed negative effects on soil salinization, which could be summarized by three possible mechanisms. The elimination of the unique pore structure in the salinesodic soil markedly reduced the ascension of the capillary water. Secondly, the DSS application significantly increased the total porosity and macroporosity in the soil. Thirdly, DSS addition enhanced the root activity and further prevented the capillary water from ascending. These findings are crucial in developing and optimizing soil reclamation strategies.