The headspace volatiles of living and picked tea rose, narcissus, osmanthus, and spearmint were examined comparatively using Tenax as the trapping adsorbent and GC/MS as the method of analysis. It was found that the living rose possessed cis-3-hexenyl acetate (20.67%) as the major volatile component, whereas the major volatile component of the picked rose was 3,5-dimethoxy toluene. Living narcissus flowers were found to contain benzyl acetate (44.0%), 3,4- and 3,5-dimethoxy toluene (35.0%), and indole (5.0%), whereas picked flowers contained benzyl acetate (30–43%), 3,4- and 3,5-dimethoxy toluene (18–39.5%), and indole (0.3–1.0%). Osmanthus flowers (living) were found to possess β-damascenone, dihydro-β-ionol, and 4-keto-β-ionone, whereas these compounds were not detected in either air or nitrogen-purged picked flowers. Finally, harvested spearmint possessed carvone (70.0%) and limonene (2.0%) in its headspace, while the headspace of living spearmint was found to contain carvone (24.0%) and limonene (18.0%). These differences demonstrate that dramatic chemical changes take place in a plant or flower once it is harvested.