A description of the methods and materials addresses the obtaining of the hair samples and the SFE-GC/MS apparatus and procedures for analyzing the hair. The comparison of this process with human identification from hair by using mitochondrial DNA (mtDNA) sequences is also described. This preliminary study, which considered a modest number of head hair samples (n=20), suggests that analysis of the surface components of small hair samples by SFE-GC/MS may help associate hair samples taken at a crime scene with those of specific individuals. MtDNA sequence analysis was performed on hair taken from 10 of the 20 individuals, who represented 4 family units. MtDNA sequences from different families were distinguishable, but DNA sequences from maternal relations were indistinguishable. The SFE-GC/MS chemical profiles for maternal relations were typically quite different and could add important complementary information to that from mtDNA sequencing data. The findings of this feasibility study generally encourage further investigation of a number of factors that could influence the chemical profile of the surface components from an individual's hair, as well as the reproducibility of that chemical profile. These factors include, but are not limited to, the location from where the sample was taken, any treatments applied to the hair by the individual, and the age of the hair sample. Subsequent studies should investigate differences in the chemical profiles of hair from adults, adolescents, and children, as well as persons of different genders and heritages. 4 tables, 5 figures, and 25 references