A current review of the application of solid-phase microextraction (SPME) to the analysis of ignitable liquids and explosive residues is presented along with experimental results demonstrating the relative effects of controllable variables. Variables discussed include fiber chemistry, adsorption and desorption temperatures, extraction and desorption times, fiber sampling placement (direct, headspace, and partial headspace) and matrix effects, including water content. SPME is shown to be an inexpensive, rapid and sensitive method for the analysis of ignitable liquids and high explosives residues from solid debris samples and from aqueous samples. Explosives are readily detected at parts per trillion concentrations and ignitable liquids are reproducibly detected at levels below those using conventional methods.