The torrefaction of municipal solid waste is one of the solutions related to the Waste to Carbon concept, where high-quality fuel—carbonized refuse-derived fuel (CRDF)—is produced. An identified potential problem is the emission of volatile organic compounds (VOCs) during CRDF storage. Kinetic emission parameters have not yet been determined. It was also shown that CRDF can be pelletized for energy densification and reduced volume during storage and transportation. Thus, our working hypothesis was that structural modification (via pelletization) might mitigate VOC emissions and influence emission kinetics during CRDF storage. Two scenarios of CRDF structural modification on VOC emission kinetics were tested, (i) pelletization and (ii) pelletization with 10% binder addition and compared to ground (loose) CRDF (control). VOC emissions from simulated sealed CRDF storage were measured with headspace solid-phase microextraction and gas chromatography–mass spectrometry. It was found that total VOC emissions from stored CRDF follow the first-order kinetic model for both ground and pelletized material, while individual VOC emissions may deviate from this model. Pelletization significantly decreased (63%~86%) the maximum total VOC emission potential from stored CDRF. Research on improved sustainable CRDF storage is warranted. This could involve VOC emission mechanisms and environmental-risk management.