Shale gas desorption and loss is a serious and common phenomenon in the Sichuan Basin. The characteristics, capability, and origin of shale gas desorption are significant for understanding the shale gas reservoir accumulation mechanism and guiding shale gas exploration. The shale gas of the Longmaxi Formation in the southeastern Sichuan Basin was studied based on a shale gas desorption simulation experiment, combined with mineral composition, total organic carbon, specific surface area, isothermal adsorption, and scanning electron microscope (SEM) data. Here, the shale gas desorption capability was quantitatively evaluated, and its controlling factors are discussed. The results show that the shale gas desorption process within the Longmaxi Formation varies significantly. The total time of the desorption process varies from 600 min to 4400 min, and it mainly occurs by the 98 °C desorption stage. The desorption capability of the lower Formation is markedly weaker than that of the upper Formation, and it is mainly determined by the shale properties. Organic matter (OM) is the most important controlling factor. As the OM content increases, the specific surface area, methane adsorption capacity, and OM pores increase, leading to a rapid decrease in shale gas desorption capability. In addition, feldspar exhibits a positive correlation with shale gas desorption capability due to its large pores but low specific surface area.