Using liquid carbon dioxide (LCO2) as a medium for underground coal fires prevention and control, while reducing the emissions of CO2, is a promising option for CO2 utilization worldwide. However, the mechanism of LCO2 flow with phase transition on coal temperature is still not clear. In this work, an experimental system was designed and fabricated to investigate the phase transition behavior and temperature variation during injecting LCO2 into pulverized coal and the impact of mass flow rate, nozzle diameter, and injection pressure on cooling effect. The results indicate that when LCO2 was injected into the pulverized coal, the instantaneous phase change into solid and vapor occurred just after leaving the release port. An intensive heat transfer process occurred because of the throttling effect, flashing effect, and sublimation and thereby formed a cooling area (<−56.6°C), which was the main area of cooling effect and phase transition; as injection time increases, the range of this area increases in the form of logarithmic function. In addition, the cooling area exhibited a strong dependence on the injection conditions, and its correlation with mass flow rate, nozzle diameter, and injection pressure are identified as exponential, logarithmic, and linear relationship by dimensionless analysis, respectively. Meanwhile, an empirical formula was developed for calculating the cooling effect under various injection conditions. In summary, the experiments provided fundamental data and regime for predicting the effect of LCO2 injection on the temperature of pulverized coal, which can be used to guide the utilization of LCO2 for coal fires prevention. © 2020 Society of Chemical Industry and John Wiley & Sons, Ltd.