To explore coal fracture propagation mechanisms, the supercritical CO2 fracturing of coal seams was simulated under true triaxial stress with various injection methods, injection temperatures, and injection flow rates. The spatial–temporal distribution of the fracture propagation and evolution was located by acoustic emission monitoring. The microcosmic action mechanism of supercritical CO2 fracturing to form fractures and its advantages over conventional hydraulic fracturing are discussed in detail. The results suggest that due to the high porosity of coal, CO2 in the local area is subject to multi-phase transitions, which makes the spatial distribution of fractures more discrete and more complex. For coal seam fracturing, supercritical CO2 can reach the fracture tip and penetrate the coal substrate more easily than water. In addition, supercritical CO2 can access smaller channels than that of water, and thus, it tends to induce secondary fractures and connect natural fractures far from the injection site.