A new, fast, and ultra-sensitive headspace sampling method was developed and coupled to the Capillary Microextraction of Volatile (CMV) device for the analysis of ignitable liquid residues (ILRs). This headspace sampling method involves the use of a heated can apparatus to aid in the recovery of volatile compounds in medium and heavy petroleum distillates. The technique was evaluated for the recovery of low mass loadings (tens of ng) of charcoal lighter fluid, kerosene, and diesel fuel. Six characteristic compounds from these ILRs were selected for recovery evaluations: nonane, decane, undecane, tridecane, tetradecane, and pentadecane. The heated can headspace sampling technique was compared to a previously reported non-heated paper cup headspace sampling technique and showed an increase in mass recoveries for 5 out of the 6 compounds. Mass recovery increases of 50-200% for undecane and tetradecane in diesel fuel were achieved in comparison to the non-heated sampling method. The average relative standard deviation (in % RSD) between the replicate trials also decreases from 29% to 6% when using the heated can method. To simulate an on-site, field protocol, ignitable liquids were spiked onto burned debris collected from a live burn exercise and the recoveries were compared using the heated can and paper cup headspace sampling techniques. This 20-minute heated sampling method was demonstrated to be made fieldable when coupled to a portable FLIR Griffin GC-MS instrument, and can allow for a full in-field sampling and analysis protocol with less than 30 minutes of extraction and GC-MS analysis.