The term 'volatile fraction' is a framework including a range of approaches and/or techniques, which produce samples that, while they may have different compositions, are representative of the volatiles characterizing a vegetable matrix, e.g. headspace, essential oils, flavours, fragrances, aromas and extracts prepared through specific techniques. Its study requires analytical methods and technologies able not only to evaluate its composition exhaustively but also to monitor variations of its profile and to detect trace components characterizing the plant being investigated. The strategies of analysis have changed significantly over the last 15-20 years because of the introduction of new approaches, in particular: (i) solventless sample preparation techniques; (ii) fast gas chromatography and related techniques; (iii) new analytical techniques, such as comprehensive gas chromatography (GC); (iv) new operative strategies based on approaches developed for other fields and applied to plant analysis; and (v) data elaboration strategies producing a higher level of information. This article is a short overview on (1) the advancement of analytical techniques and how they can influence strategies and approaches to study the plant volatile fraction, and (2) enantiomer GC and GC-mass spectometry separation using cyclodextrins as chiral selectors.