A comparative study of traditional simultaneous distillation extraction (SDE), microwave assisted hydrodistillation extraction (MWHD) and ultrasound-assisted extraction (USE) is presented, for the extraction of essential oils from fresh garlic (Allium sativum) cloves. Each method is evaluated in terms of qualitative and quantitative composition of the isolated essential oil. The highly reactive sulfur molecules of the garlic volatile fraction show variable response to the different isolation methods. The application of ultrasound for the extraction of the essential oil is considered to cause a lesser damage of thermal-sensitive molecules, thus, providing a better approach of the compounds primarily responsible for the characteristic odor and taste of freshly chopped garlic. All heat-involving isolation procedures have been shown to differentiate the volatile-fraction profile as analyzed by GC-MS. Especially when grouping the compounds into cyclic and acyclic, the percentage concentrations drop from 77.4% to 8.7% for the acyclic while that of the cyclic compounds increase from 4.7% to 70.8%. The observed fact may be attributed to the effect of the heat applied, which changes from harsh thermal treatment (SDE) to short time thermal (MWHD) and room-temperature isolation (USE). The use of USE proves to be crucial in order to provide reliable insight into garlic's chemistry.