Garlic (Allium sativum L.) is highly consumed worldwide. This crop is mainly known for its flavor and odor, although the many medicinal properties that are attributed to it, including anticarcinogenic, antiatherosclerotic, and antithrombotic potential, among several others, have called the attention of scientists since very early times. It is known that sulfur-containing volatiles are the principal compounds responsible for such properties. The aims of this work were to develop a solventless extraction method for sulfur-containing volatiles from garlic, as well as their chemical characterization. Since garlic volatiles are rather thermolabile, low-pressure hydrodistillation was chosen as the extracting method. The analysis of all compounds was performed on an HP-FFAP chromatographic column mounted in a GC-MS system. For volatile transfer and injection method, solid-phase microextraction was selected, with the use of eight different fibers. The most abundant volatile compound was diallyl disulfide, followed by diallyl trisulfide. Among the 47 totally identified compounds, 18 were linear sulfur-containing volatile compounds, 6 were of non-sulfur nature, and the other 23 were cyclic compounds. However, linear sulfur volatiles accounted for 94% of the total amount.