The interactions of coal with CO2 at pressures of up to 30 bar concerning mechanisms of diffusion, the strength of interactions, and the irreversibility of uptake for the permanent disposal of CO2 into coal fields have been studied. Differential scanning calorimetry was used to investigate coal/ CO2 interactions for North Dakota, Wyodak, Illinois No. 6, and Pittsburgh No. 8 coals. It was found that the first interactions of CO2 with coals led to strongly bound carbon dioxide on coal. Energy values attributed to the irreversible storage capacity for CO2 on coals were determined. The lowest irreversible sorption energy was found for North Dakota coal ( 0.44 J/ g), and the highest value was for the Illinois No. 6 coal ( 8.93 J/ g). The effect of highpressure CO2 on the macromolecular structure of coal was also studied by means of differential scanning calorimetry. It was found that the temperature of the second- order phase transition of Wyodak coal decreases with an increase in CO2 pressure significantly, indicating that high- pressure CO2 diffuses through the coal matrix, causes significant plasticization effects, and changes the macromolecular structure of the Wyodak coal. Desorption characteristics of CO2 from the Pittsburgh No. 8 coal were studied by temperature- programmed desorption mass spectrometry. It was found that CO2 desorption from the coal is an activated process and follows a first- order kinetic model. The activation energy for CO2 desorption from the Pittsburgh No. 8 coal increased with the preadsorbed CO2 pressure, indicating that CO2 binds more strongly and demands more energy to desorb from the Pittsburgh No. 8 coal at higher pressures.