This chapter provides a review of solid-phase microextraction (SPME) applications in forensic studies including analytical toxicology, explosive detection, instrumental analysis of human scent, and detection of chemical warfare agents. The most recent trends within this analytical technique are discussed. As SPME successfully integrates a number of analytical steps such as sampling, extraction, preconcentration, and sample introduction for instrumental analysis, which are both laborious and time consuming, making the sample preparation and instrumental analysis relatively faster, SPME has gained enormous popularity among forensic scientists in recent years. Recent trends in the advancement of the extraction process including novel fiber coatings and in vivo sampling applications are described and a detailed discussion on important chemical analysis needed in the forensic laboratory for use in criminal investigations is presented. Highlights of the SPME process encompass recent novel applications such as the detection of chemical warfare agents and the identification of volatile organic signatures of live human scent for potential biometric measurements. The future of SPME methods lies in the development of more rugged fiber prototypes that can provide enhanced selectivity to the coatings as well as high thermal and solvent stability when performing complex analysis.