Oily sludge is a loose material containing solid and multiple liquid components. Thermal desorption is an efficient method of disposing of liquids from oily sludge. Most existing studies have mainly discussed the effect of some external process parameters on thermal desorption, with little discussion on the heat transfer characteristics and the variation in the wet component mass of oily sludge under heating. Small-scale experiments have been performed to measure the rise in temperature and liquid phase content change of the sludge during heating. The temperature rise rate increases with material density and increases faster during the initial heating stage, while it slows down as the liquid phase evaporates. The adhesive shear stress is determined by measuring the pulling force of the test rod, which decreases with decreasing water content and increases significantly with decreasing oil phase content. Heat transfer and energy distribution models have been developed to calculate the rise in the temperature of materials and the evaporation of contained liquids. The heat and mass transfer processes are obtained from simulation calculations by taking the initial material with a mass content of 25% water and 10% oil under a heating temperature of 500 °C. When the heating time reaches 135 min, the drying region reaches the boundary of the test container, at which the material temperature exceeds 350 °C. During the evaporation of different liquid-phase components, there are multiple segments in the corresponding temperature curves. The processing time and heat source temperature can be reasonably determined by analyzing the temperature rise of the material, and the effect of the disposal of liquids from oily sludge can be predicted by analyzing the changes in liquid content. The results may guide the formulation of process parameters for engineering project schemes for oily sludge disposal.