The effect of hydrothermal coupling on the risk of spontaneous combustion of coal (SCC) soaked at different water temperatures was studied. The results showed that the porosity and permeability of coal increased significantly after immersion in water at different temperatures. The increase at a water temperature of 30 °C was the largest, the porosity was 22.77% higher, and the permeability was 3.44 times that of raw coal. The relative content of oxygen-containing functional groups, aliphatic functional groups, and hydroxyl functional groups reached 1.8−4.5, 1.1−4.4, and 0.7−1.48 times that of raw coal after soaking in water at different temperatures. The increase ratio of functional groups is the largest under the water temperature of 30 °C. The activation energy of coal samples soaked at water temperatures of 30 and 45 °C decreased by 9.4 and 2.9%, respectively. Under the condition that the coal sample temperature was lower than 110 °C, the highest oxygen consumption rate and heat release rate were coal samples soaked at water temperatures of 30 °C, and the lowest was raw coal. When the coal temperature was higher than 170 °C, all coal samples soaked in different water temperatures are higher than that of raw coal, and the water temperature of 30 °C is the highest. The risk of spontaneous combustion of coal is highest after long-term soaking at 30 °C water.