Objectives: Benzene is commonly emitted in several industries, leading to widespread environmental and occupational exposure hazards. While less toxic solvents have been substituted for benzene, it is still a component of petroleum products and is a trace impurity in industrial products resulting in continued higher occupational exposures in industrial settings in developing countries. Materials and Methods: We investigated the potential use of an electronic nose (e-nose) to monitor the headspace volatiles in biological samples from benzene-exposed Egyptian workers and non-exposed controls. The study population comprised 150 non-smoking male workers exposed to benzene and an equal number of matching non-exposed controls. We determined biomarkers of benzene used to estimate exposure and risk including: benzene in exhaled air and blood; and its urinary metabolites such as phenol and muconic acid using gas chromatography technique and a portable e-nose. Results: The average benzene concentration measured in the ambient air of the workplace of all studied industrial settings in Alexandria, Egypt; was 97.56±88.12 μg/m3 (range: 4.69–260.86 μg/m3). Levels of phenol and muconic acid were signifi cantly (p < 0.001) higher in both blood and urine of benzene-exposed workers as compared to non-exposed controls. Conclusions: The e-nose technology has successfully classifi ed and distinguished benzene-exposed workers from non-exposed controls for all measured samples of blood, urine and the exhaled air with a very high degree of precision. Thus, it will be a very useful tool for the low-cost mass screening and early detection of health hazards associated with the exposure to benzene in the industry.