Wood pellets produced from fresh sawdust can form and release uncontrolled gases during bulk storage, a tendency referred to as off-gassing. This study investigated the off-gassing tendencies of Scots pine wood pellets made from separated sapwood and heartwood sawdust. The effects of drying temperature, raw material storage, as well as varying proportions of sapwood and heartwood were also investigated. There was a strong linear correlation between off-gassing and sapwood content, with correlation coefficient (R) values greater than 0.9 at p < 0.001 for all the off-gases. An increase in sapwood content of the feedstock led to a significant increase in off-gassing of CO2, CO, and CH4, and O2 consumption. The drying temperature of the raw material had a significant effect on off-gassing of both sapwood (F (8, 26) = 51.32, p < 0.05) and heartwood (F (8, 26) = 334.1, p < 0.05) pellets. Increasing the drying temperature for heartwood resulted in increased off-gassing, while for sapwood, the off-gassing reduced. Storage of sapwood raw material before pelletization reduced the off-gassing of wood pellets, whereas for heartwood, it had no significant impact. Based on the results, it is suggested that a biological process, in combination with the chemical oxidation of fatty acids, lay behind the off-gassing of wood pellets.