The way aroma is released during eating is critical to a food's sensory character, and is largely determined by the structure and composition of the food matrix. The impact of food structure and composition on in vivo volatile release and corresponding perception were systematically characterized using a standardized consumption and breathing protocol with a human panel (n = 8). Everyday foods (n = 12) representing a range of liquid, semi-solid and solid states, and varying in texture and composition (fat content) were selected. Target volatiles released during eating were measured in exhaled nostril air using a proton transfer reaction mass spectrometer and the corresponding sensory stimulus was rated using continuous time intensity. Release parameters such as the Tmax and area under the concentration curve for pre-swallow and post-swallow eating phases were compared across foods. Differences in release and time intensity were measured according to structure – liquid, semi-solid and solid – as well as composition, such as fat content. Post-swallow release was dominant in liquids, greater pre-swallow release was characteristic of solids and semi-solids released equally in both phases. Systematic differences in Tmax as a result of food structure as well as composition were measured. In general, Tmax increased from liquid to solid and was longer in high fat foods. Inter-subject variability in volatile across the range of food types is discussed. The data provided insights into the relationship between food structure and composition and volatile release; application of this approach may help guide the development of novel food products. Copyright © 2012 John Wiley & Sons, Ltd.