The free and bound volatiles of tobaccos were analyzed by capillary GC and GC-MS. Bound volatiles were isolated by dichloromethane extraction followed by stream distillation continuous extraction (SDE) at pH 2.5 acid hydrolysis. The bound aromatic compounds were hydrolyzed by acid at pH 2.5, and the bound volatiles were liberated and extracted into dichloromethane by SDE simultaneously. In total, 23 volatiles were identified, with neophytadiene, 2-ethyl hexanol, damascenone, benzene ethanol, palmitic acid, stearic acid, linoleic acid, farnesyl acetone, 3-oxo-ionol, and megastigmatrienone being the major components. They consisted mainly of compounds exhibiting aromatic characteristics. The quality and quantity of free and bound volatiles exhibited different distributions in uncased or cased tobaccos. The volatiles existed in higher amounts in bound form than in free form. Compared with uncased tobaccos, free form volatiles showed a decrease after the casing process, while bound volatiles showed an increase.