Solid phase microextraction (SPME) is a very versatile, convenient and simple technique of sample preparation for chromatographic analysis. SPME finds increasingly wide acceptance in the isolation and enrichment of chemical warfare agents (CWAs) and their degradation products in air, water and other liquid samples (e.g. urine), soil, clothing material, etc. for their gas chromatographic (GC) determination. Until now, typical commercially available fibers have mainly been used for the extraction of CWAs in direct immersion and headspace modes, although attempts were made to introduce new fiber coatings, characterized by higher selectivity towards the analytes of interest. The combination of SPME and GC enables reaching low detection limits dependent on the analyte, matrix, detection system, etc.; for example, single ppb for benzilic acid in soil and nerve agents in aqueous samples and 200 ppb for thiodiglycol, a degradation product of sulfur mustard.