The volume has as primary focus multidimensional gas chromatography (heart-cutting systems, comprehensive 2D-GC systems and hybrid solutions) and its characteristic features for in depth investigation of complex fractions of odor-active volatiles. Contributions, from outstanding researchers in the field from Academia and industry, cover fundamentals aspects on the physiology of olfaction, the strategies to identify key-odorants from the bulk of detectable volatiles (sensomics), the principles of operation of multidimensional analytical platforms (i.e., comprehensive two-dimensional gas chromatography – GC×GC; heart-cut 2D-GC, hybrid systems), and the fundamental role of mass spectrometry in providing reliable and informative data. Insights on new systems design and configurations are also provided, including sample preparation and data processing strategies, as important steps of the whole analytical process. Real-world examples cover food volatiles, complex aroma mixtures, odors emitted from industrial plants, volatiles of interest in forensic and medical applications.