Multidimensional separation in gas chromatography (MDGC) plays an important role in chemical analysis. This review presents selected literature on MDGC development and examples of the range of functionality reported for MDGC methods over the past 2 decades. With the most obvious advantage of providing much greater capacity for resolving constituents of a sample, MDGC extends analytical efficiency to a more substantial molecular coverage, combined with operational flexibility. But by judicious choice of implementation method, important chemical information relating to the sample, its components, potentially physico-chemical properties, and improved capacity for absolute identification may be realised. Sample-to-sample comparison is improved, and sample characterisation is facilitated especially when MDGC is combined with the informing power of modern mass spectrometry. Innovative MDGC arrangements allow high resolution coupled with spectroscopy and alternative bioassays, and delivers molecular elucidation in ways that are beyond just simple analysis of volatiles.