In spite of the importance to the use of organic solvents in the shoes industry, exposure data of the employees at these solvents in this sector are absent in Tunisia. The objective of this study is to establish a biotoxicological supervision of exposure in shoes manufacturing companies. After the inventory of the most dominant solvents (acetone, cyclohexane, hexane and methylethylketone, toluene) in the preparations used in shoes manufacturing, 18 voluntary companies benefited from 55 dynamic atmospheric samplings realized on a duration of 4 hours. The exposure index some mixture ranged between 0.1 and 8.8 and presented an average value superior to 1, mainly in the partly industrialized process. These values reached, respectively, 1.7, 2.5 and 4.5 for the posts of finishing, shoes collector and glues dispatcher. The atmospheric average concentrations of certain solvents exceeded the limit value of professional exposure mainly for the hexane with a value of 214 mg/m3 in certain posts. The chronic exposure to organic solvents in a shoes industry and to establish a first report on the profiles of exposure to these solvents in this sector. Hence, an approach of evaluation of the professional risk by the biotoxicological supervision of exposure is established in Sfax city.