Chromatography is a process for the separation of compounds from the mixtures. Gas chromatography (GC) is one of the most important and common techniques in separation science. The main focus of this chapter is to demonstrate a hands-on approach to preparative gas chromatography (Prep-GC) technique and its use for the isolation of natural products, particularly terpenes and other volatiles. Starting from the classification of GC separations, columns, and stationary phases, sampling techniques, mobile phases, detectors, and fraction collector systems of analytical and preparative gas chromatographic separations are comparatively covered in this chapter.