This data set contains raw data files for ignitable liquids, mock fire debris samples, and other related samples. All samples were extracted using solid phase microextraction (SPME) and analyzed by rapid gas chromatography-mass spectrometry (GC-MS), a recently developed chromatographic screening technique. Data is included for instrument inlet optimization, analysis of neat ignitable liquids (gasoline and diesel fuel), and analysis of mock burn samples consisting of carpet and wood substrates spiked with either ignitable liquid. Using the optimized instrumental method, compounds commonly utilized for classification of both ignitable liquids were identified in the respective neat samples and mock burn samples. This data supports work to demonstrate the successful implementation of SPME with rapid GC-MS for a fast analytical screening workflow for fire debris applications.Certain commercial equipment, instruments, or materials are identified in this dataset in order to specify the experimental procedure adequately. Such identification is not intended to imply recommendation or endorsement by the National Institute of Standards and Technology, nor is it intended to imply that the materials or equipment identified are necessarily the best available for the purpose.