AbstractUsing a non‐equilibrated solid‐phase microextraction/gas chromatography/mass spectrometry technique, differentiation between a wide variety of types and examples of artificial flavors has been demonstrated. Addition of an internal standard to the samples, as received, allowed for the calculation of yields on a µg g−1 basis for the majority of headspace volatiles. The relative standard deviation values expressed as percentages were between 3 and 5%. The precise nature of the approach coupled with the compound identification capacity of the mass spectrometer afforded the capability to easily differentiate between multiple sources of artificial flavors. With a total analysis time of approximately 30 min and the absence of solvent, this approach has the capability of detecting and quantifying the presence of the low‐molecular‐weight solvents often used in the preparation of artificial flavors. Such a capability represents a distinct advantage over more conventional methods of solvent dilution. Results from conventional gas chromatography/mass selective detector analyses are contrasted and compared with the results obtained from the headspace SPME approach. Copyright © 2005 Society of Chemical Industry