Thermal-enhanced soil vapor extraction (T-SVE) is an in-situ remedial technique that can address the limitations of contaminant mass transfer and soil permeability. The relative humidity of the injected air, heating temperature of the thermal well, extraction pressure, and extraction mode are important design parameters of a T-SVE system that determine the temporal and spatial distributions of soil temperature and removal rate. Using a thermal–hydraulic–chemical coupled model with the interphase mass transfer of contaminants and water evaporation/condensation, this study investigated the effects of relative humidity, heating temperature, extraction pressure, and extraction mode on T-SVE performance. The results showed that with an increase in relative humidity, the heating temperature of the contaminated soil significantly improved; however, the removal rate of contaminants decreased, particularly in the late stage of remediation. Considering the heating temperature of the thermal well, a critical air relative humidity value that significantly affects the removal rate of contaminants was observed. The heating temperature of the thermal well must be considered in engineering design; however, the evaluation of the relative humidity of the air cannot be ignored.