Liquid carbon dioxide (LCO2) could potentially be utilized in coal gasification plants for effectively transporting coal particles, replacing conventional carriers such as water (H2O), particularly in wet-fed gasifiers. However, it is essential to understand the atomization behavior of LCO2 leaving an injector nozzle under both coal-free and coalfed conditions. We examined the atomization behavior of a coal-LCO2 slurry during the throttling process. The injector nozzle was mounted downstream of a high-pressure spray system. The effect of upstream pressure on flash atomization and devolatilization behavior was presented. Compared with the coal-LCO2 mixture, the spray pattern of the coal-water mixture was significantly different, since it evidenced a Rayleigh-type breakup mode. This difference indicates that the coal-water slurry did not transport the coal as effectively as the coal-LCO2 slurry.