The development of novel non-destructive methodologies for the verification of electronic component authenticity is imperative in reducing the economic and safety risks associated with the use of counterfeited products. Currently, inspection methods rely on a series of electrical and physical tests that usually are labor intensive, destructive, and still not 100% effective, given their dependence on human interpretation. In this paper, the authors present an alternative method using solid-phase microextraction (SPME) and comprehensive two-dimensional gas chromatography with electron ionization time-of-flight mass spectrometry (GCxGC/EI-TOF-MS) to chemically characterize electronic components. The novel approach outlined in this study utilized the high sensitivity of GCxGC/EI-TOF-MS systems to consistently identify more than 300 volatile markers in two different groups of 14-pin, 16-bit microcontrollers and one group of 16 GB microSDs from three different manufacturers. Results showed that the chemical characterization of the electronic components was effective, repeatable, and non-destructive. The significant volatile markers were found to be dependent on the manufacturer, age, and type of electronic component. Thus, the list of significant volatile markers of each electronic component could potentially serve as a basis for verifying the source of an electronic component. Compared to existing physical verification methods, this novel approach is faster and less ambiguous, and avoids the overlook or false identification of counterfeits. In fact, this methodology could potentially indicate if further inappropriate manipulations have taken place on the component, based on the presence and quantity of 1,3,5-cycloheptatriene, thereby reducing the risk of counterfeit components being installed in electronic systems. Using GCxGC/EI-TOF-MS and SPME techniques may be helpful in reducing the quantity of counterfeit electronic components found in warfare systems used by the United States Department of Defense (DoD), which is especially at risk, due to the rapid aging of deployed systems and a vast span of interconnected logistics supply chains that provide components for installation in such warfare systems.