The development of SPME over the past 20 years, and the more recent wide availability of automated SPME systems, has generated renewed interest in derivatization with gas chromatography for the analysis of highly polar or labile analytes. By using an SPME fiber as the extracting phase, the derivatization process is straightforward and readily automated. From anecdotal examination of the literature, it appears that the fiber may offer benefits over traditional liquid phase reactions in that control over the selectivity of the reaction for the desired product and fewer interfering byproducts may be more readily achieved. Nearly all authors have reported that SPME-based derivatization methods provide equivalent or superior analytical performance to their traditional counterparts. While attention to derivatization in general has waned among gas chromatographers, the advent of procedures in combination with SPME makes derivatization again attractive and worthy of consideration in analytical method development.