The flame retardant Hexabromocyclododecane (HBCD) is part of the critical emerging contaminants. The diet is the major route of human exposure to HBCD and consumers may be exposed through a single food intake at very high doses. The only way to guarantee their food safety given the unpredictable isolated cases of high contamination is to propose frequent and large-scale controls, yet the current reference analytical methods are economically inconceivable. Alternative approaches based on targeted quantification of livestock's exposure markers to pollutants are proposed. Among the compounds assumed as potential markers, the volatile organic compounds (VOCs) are particularly promising. Based on animal test involving laying hens contaminated or not by HBCD through their feed, the present study demonstrates the relevance of using solid phase microextraction-gas chromatography-mass spectrometry (SPME-GC-MS) for profiling VOCs in animal-derived products and for determining the markers of HBCD exposure. The volatile fingerprints of egg yolk and liver allowed the different animal groups to be clearly discriminated and volatile markers of HBCD exposure to be pointed out. The analysis of these markers could enable to reveal systematically suspect samples on market and to guide further analyses to confirm and possibly explain the contamination.