Solid-phase microextraction (SPME) was developed in 1989 [24] and is a solventless extraction and which has been used to identify petroleum products in real arson-suspected fire debris samples [9,25–33]. SPME is an excellent alternative for traditional extraction techniques, and can be divided into Direct Immersion (DI-SPME) and Headspace (HS-SPME) types, depending on where the fiber is situated. Many of the advantages of SDME also apply here, for example SPME reduces the extraction time by 10–20 min in comparison with activated char- coal strips (ACS) [34], shows greater sensitivity in detecting gasoline in a study at levels where other passive methods have failed [29] and is unaffected by interferences from the pyrolysis products of wood and plastics [35]. In addition headspace sampling eliminates interfer- ences, can be used when aqueous media are present and has the ability to be used in the field. Therefore in fire investigation, HS-SPME is poten- tially useful due to complex matrix composition and potentially high water content. DI-SPME has been applied to the recovery of accelerants and explosives from aqueous samples [36,37], but a SPME method has not been reported so far. Water samples represent 5% of all samples for fire investigation [9] and liquid matrix membrane SPME has been applied to complex and dirty matrices [38]. Direct-contact SPME has been applied to soil by Yoshida et al. [39], with the technique also used for identification of ignitable liquids from human skin [27]. The SPME method, compared with traditional LLE, limits loss of petroleum products during the sampling procedure since the process incorporates extraction, concentration and injection into a single step, which, in turn, makes it more time efficient. Additionally, the HS mode provides a lon- ger lifetime of the fiber and protects the fiber from any adverse effects that may occur due to non-volatile, high molecular weight substances in the real samples. This allows determination of petroleum products in low levels of concentrations with greater accuracy and precision.