Solid phase microextraction (SPME) has emerged as a rapid alternative to conventional sample extraction techniques. SPME can be used in solids, liquids, and sample headspace. Compounds are sorbed by a stationary phase coated on a fused silica fiber. The compounds are desorbed, and analyzed using gas chromatography (GC), and high performance liquid chromatography (HPLC). As a part of the present work we have found that SPME can also be used conveniently with ion mobility spectrometry (IMS). Cocaine and heroin vapors sorbed on a SPME fiber were detected using IMS. The use of SPEE-GC or SPME-HPLC has been reported in analysis of urine samples containing cocaine and its metabolites. We are evaluating SPME-IMS, and SPME-GC systems for the detection of cocaine and heroin and their decomposition products in the headspace above surfaces. This is part of our research on the surface decomposition of contraband drugs for detection applications. This paper will give a variety of examples in the use of SPME in the detection of contraband drugs and their reaction/decomposition products in the vapor state. An example is the detection of cocaine in the headspace above cocaine HCl at room temperature.