Most amine salts of amphetamine-type drugs are not directly amenable to headspace recovery using SPME due to their high polarity and low vapor pressure. SPME is now an important technique for a wide range of analytical applications, including forensic drug chemistry. This study explored techniques that might expand the scope of SPME as applied to forensic drug analysis. It explored the possibility of developing a method for deprotonation of amine salts that does not involve conventional solution-phase acid-base chemistry and has the capability for integration with SPME. It was felt that SPME in combination with derivatization would offer some advantages over standard methodologies. Alkylchloroformates were chosen as derivatization reagents because they appeared to offer some useful characteristics, such as being reactive towards amines and inactive towards water, alcohols, and other oxygen-based nucleophiles. A new development of SPME is presented that allows rapid, comprehensive screening of evidentiary material for the presence of amphetamine-type drugs, their precursors, and manufacturing by-products. The process has direct application in the screening of “difficult” evidentiary material such as banknotes, clandestine laboratory documents, or garments. The headspace method is less invasive to the sample and much more convenient. Detection limits achieved are quite appropriate for the task of recovering traces of drugs, and more than sufficient for screening visible quantities of powder or tablets. The technique covers a wide range of compounds; it is well suited to intelligence gathering, source comparison, and identification of synthetic pathway. 11 figures, 17 references