In this study, the effects of origin (Chinese, France, and America), intensity of toasting, and degree of charring on the volatiles of oak whisky barrels were comprehensively investigated via liquid–liquid extraction–gas chromatography–mass spectrometry (LLE–GC–MS) combined with multivariate statistical analysis. Results of principal component analysis (PCA) showed that the main oak–derived volatiles in oak were more influenced by origin and toasting than by charring. French oak had a higher content of volatile compounds than the other two origins, and this difference decreased with toasting and charring. The process of toasting and charring was important for the release of volatile compounds from oak. The content of most oak–derived volatiles increased with deeper toasting intensity, and the degree of charring promoted or inhibited the release of oak–derived volatiles. The volatile components in oak blocks were affected by the two–factor interaction of toasting and charring. Continuing the process of the charring of oak at a certain level of toasting may have an enhancing or diminishing effect on the content of different volatile compounds, depending on the circumstances.