This narrative review examines the complex relationship that exists between the presence of specific configurations of volatile organic compounds (VOCs) in food and drink products and multisensory flavour perception. Advances in gas chromatography technology and mass spectrometry data analysis mean that it is easier than ever before to identify the unique chemical profile of a particular food or beverage item. Importantly, however, there is simply no one-to-one mapping between the presence of specific VOCs and the flavours that are perceived by the consumer. While the profile of VOCs in a particular product undoubtedly does tightly constrain the space of possible flavour experiences that a taster is likely to have, the gustatory and trigeminal components (i.e., sapid elements) in foods and beverages can also play a significant role in determining the actual flavour experience. Genetic differences add further variation to the range of multisensory flavour experiences that may be elicited by a given configuration of VOCs, while an individual's prior tasting history has been shown to determine congruency relations (between olfaction and gustation) that, in turn, modulate the degree of oral referral, and ultimately flavour pleasantness, in the case of familiar foods and beverages.