The process of soil moisture phase transitions (SMPT) under freeze–thaw cycling is considered a key factor driving changes in soil pore structure. However, there is still no consensus on which indicators related to SMPT affect the soil pore structure. The objectives of this study were to compare SMPT and soil pore characteristics under freeze–thaw cycling, and to analyze the inherent relationship between them as affected by different bulk densities. Hence, we employed thermal pulse time-domain reflection technology (T-TDR) and X-ray CT scanning technology (X-CT) to quantitatively study the process of SMPT and pore characteristics of soil core samples (60 mm diameter, 100 mm height) repacked with three different bulk density levels: 1.10 g·cm−3 (NC), 1.30 g·cm−3 (LC) and their combination (1.10 g·cm−3 for upper half, 1.30 g·cm−3 for lower half, SC) under freeze–thaw cycling. Our results showed that compared with NC, the porosity of LC’s 0–5 cm soil column decreased by 0.070 cm3·cm−3, the imaged porosity (ϕ>60μm) decreased by 0.034 cm3·cm−3, and the maximum soil ice content (MIC) decreased by 0.030 cm3·cm−3. The pores within the range of 200−300 mm (ϕ2) and 300–400 mm (ϕ3) contribute the most significantly to ϕ>60μm (50–60%). Soil initial moisture content (IMC) and MIC explained 50.1% of the change in ϕ2, and the bulk density explained 49.3% of the change in ϕ3. During the melting process, higher moisture content promotes the thaw collapse of soil particles, resulting in a decrease in ϕ>60μm. The mean pore radius of the limiting layer (MRLL) and the hydraulic radius (HR) show that changes in bulk density from 1.10 g·cm−3 to 1.30 g·cm−3 do not have significant differences. Our results show the relationship between SMPT and pore structure change during freeze–thaw cycles as affected by initial soil bulk density and moisture condition.