It is known that polar solvents swell coal, break hydrogen-bonds in the macromolecular structure, and enhance coal liquefaction efficiencies. The effects of drying, interaction with supercritical CO2 and degassing on the physical structure of coal have been studied using gas sorption technique and a scanning electron microscope (SEM). Both drying and interaction with supercritical CO2 drastically change the micropore and mesopore surface area, absolute volume, and volume distribution in both bituminous coal and lignite. Degassing removes debris in the pore space which allows for better analysis of the changes in the morphology that were induced by drying and exposure to supercritical CO2. SEM reveals that interaction of bituminous coal with supercritical CO2 results in an abundance of carbon structures similar to the maceral collinite.