Imaging time-of-flight secondary ion mass spectrometry (SIMS) was used to evaluate the detection of contaminant chemicals on the surfaces of single synthetic textile and canine hair fibers. The results of the study showed that a variety of chemical classes can be detected. Both cocaine and heroin could be easily observed as intact protonated molecules ([M + H]+) in the cation spectra acquired from textile fibers. Two organophosphates were evaluated: malathion, which is a common pesticide, and pinacolyl methyl phosphonic acid (PMPA), which is the principal degradation product of the nerve agent soman (a close relative of sarin). Malathion could be observed as (CH3O)2P(equalsS)S-, which is formed by thiophosphate cleavage of the intact malathion. PMPA is observed as the conjugate base ([PMPA - H]-). Surfactant chemicals found in hair care products were successfully detected on single hair fibers. Specifically, alkyl sulfates, ethoxylated alkyl sulfates, silicones, and alkylammonium compounds could be readily identified in spectra acquired from single hair fiber samples exposed to shampoo and/or conditioner. Generally, the results of the study show that imaging SIMS is applicable to single fiber analysis, for a range of adsorbed compound types. The forensic application of this instrumental approach has not been widely recognized. However, the ability of the technique to acquire specific chemical information from trace samples clearly points to applications where the need for chemical analysis is great, but the amount of sample is limited.