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A study was done in order to determine how the sampling conditions can influence the quantitative measure of PAHs in air, done with a solid-phase microextraction device. The PAHs studied were naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, fluoranthene, pyrene. A comparison between static and dynamic samplings and a plan of experiments were done to study the influence of the gaseous flow, the exposure time, and the number of PAHs in sample, on the mass trapped on the fiber. Then, the performances of PDMS 100 µm and 7 µm fibers for the extraction of PAHs in air were compared. The mass trapped by the fiber, the equilibrium time, the reproducibility, and the performances of the fiber in a dynamic sampling were also tested and compared.