This paper shows the use of exhaled air as a biomonitoring method to assess perchloroethylene (PERC) environmental and occupational exposure. A sensitive, fast, and solvent free analytical method was developed to determine PERC in ambient and exhaled air of individuals occupationally exposed. The developed method used cold fiber solid phase microextraction (CF-SPME) as the sampling technique, and a standard permeation method to simulation of air matrix. The analysis were conducted by gas chromatography coupled to mass spectrometry (GC/MS). The methods were validated and were found to be precise, linear and sensitive for environmental and biological monitoring. The developed methods were applied to twenty-seven sampling points spread across Belo Horizonte city, Brazil, twenty four dry cleaners, an electroplating industry, a research laboratory, and an automotive paint preparation shop. The results of ambient air analyses ranging from 14.0 to 3205.0 μg m−3 with median concentration of 599.0 μg m−3. Furthermore, sampling of exhaled air of individuals occupationally exposed presented results ranging from 6.0 to 2635.0 μg m−3 with median concentration of 325.0 μg m−3. The strong correlation observed between ambient and exhaled air (r =0.930) demonstrates that exhaled air is a suitable biomarker for evaluating occupational exposure to PERC.