This paper discusses results of a supercritical fluid extraction-gas chromatography/mass spectrometry (SFE-GC/MS) study of small samples ( 100 microg to 1 mg) of human scalp hair. The method offers a number of benefits including greater sensitivity than liquid extraction methods because the entire extractable mass is transferred to the analytical system, compared with only a few percent from a conventional liquid extraction/injection. The project's goals were to determine if SFE-GC/MS analyses of the surface-extractable components of an individual's hair yield consistent chemical profiles and to investigate if the profiles are sufficiently different to distinguish them from those of other individuals. In addition, the mtDNA sequences from ten of the same individuals used in the SFE-GC/MS study from four family units were determined, and, while the families were distinguishable, the maternal relations yielded identical sequences. In tandem, SFE-GC/MS and mtDNA techniques may provide valuable complementary data from forensic hair samples.