Hexabromocyclododecane (HBCD) is a critical emerging brominated flame retardant to which consumers can be exposed at high doses through a single food intake. Based on an animal experiment involving 3 groups of laying hens fed during 70 days with a control diet or gamma-HBCD-contaminated diets at 0.1 or 10mug gamma-HBCD g-1 feed, this study aims to use the volatolome of biological samples for revealing markers of livestock exposure to HBCD. Liquid chromatography-tandem mass spectrometry was used to monitor the time-course of HBCD levels in bodily samples. Each liver was analyzed by solid-phase microextraction-gas chromatography-mass spectrometry for volatolome profiling. After 70 days, gamma-HBCD concentrations in egg yolk, fat, liver and serum reached 54±4, 85±6, 31±6, and 32±4ngg-1 lw, respectively, for the low exposure level and 4.6+/5.7, 7.8+/6.5, 3.9+/3.0 and 3.9+/6.1mugg-1 lw, respectively, for the high exposure level. Isomerization of gamma-HBCD into alpha- and beta-HBCD was observed in all tissues, at least for the high exposure level. Volatolome data allowed a significant discrimination between control and exposed animals whatever the feed contamination load, demonstrating a liver metabolic response to gamma-HBCD exposure. The relevance of the twenty nine volatile exposure markers tentatively identified was discussed in light of literature data.