A SPME-GC-MS method was adapted and validated in order to quantify 5 megastigmatrienones and related odorous compounds from oak wood: guaiacol, cis-whisky lactone, trans-whisky lactone, gamma-cnonalactone, eugenol, vanillin, and acetovanillone in a single run. The five megastigmatrienone isomers (tabanones) were quantified, for the first time, in Cognac, Armagnac and rum, as contributors to tobacco-like aromas. Spirits aged in oak barrels contain higher amounts, but megastigmatrienones are also present in freshly-distilled spirits. Statistical analysis revealed that freshly-distilled and barrel-aged spirits were differentiated by their megastigma-4,7E, 9-trien-3-one levels. The Armagnac and Cognac samples were distinguished by their concentrations of the megastigma-4,6Z, 8E-trien-3-one isomer.