The aim of this work was to reliably identify odour-active compounds in dry-cured ham using powerful analysis methods for the volatile fraction. For this purpose, dynamic headspace gas chromatography combined with eight-way olfactometry using a panel of eight sniffers was used. One- and two-dimensional gas chromatography coupled with mass spectrometry and (or) olfactometry were also used. More than 600 compounds from the volatile fraction of dry-cured ham were identified and their biochemical origins are discussed. They covered a wide diversity of structures and chemical functions. Only 29 of them proved odour-active. Comparison of the results of GC–O analysis with those obtained by orthonasal sniffing of the dry-cured ham helped to gain a better understanding of how these substances contributed to the overall aroma of the product. Thus, “Fruity–Floral”, “Green–Vegetable” or “Plastic–Chemical” odours intensively perceived by GC–O have been poorly perceived by orthonasal sniffing. By contrast, “Animal–Meat products” or “Butter–Lactic–Cheesy” odours have been much better perceived by orthonasal sniffing. These results indicate that to understand the interactions between odour-active compounds, experimental doping with carefully selected odour-active compounds will be necessary.