This analytical method is a validated measurement procedure for the determination of six semi‐volatile polycyclic aromatic hydrocarbons (PAH) from the EPA list (US Environmental Protection Agency) such as benzo[
b
]fluoranthene, benzo[
k
]fluoranthene, benzo[
a
]pyrene, dibenzo[
a,h
]anthracene, benzo[
ghi
]perylene, indeno[1,2,3‐cd]pyrene and also benzo[
e
]pyren in workplace air averaged over the sampling period after personal or stationary sampling. Sampling is performed by drawing a defined volume of air through a Teflon filter, which is inserted in a GSP sampling system. The collected PAH components are extracted with a mixture of acetonitrile/methanol and analysed by means of high performance liquid chromatography (HPLC) with fluorescence detection. The quantitative determination of the PAHs is based on calibration functions obtained by means of multiple‐point calibrations. The limit of quantification for an individual PAH is in the range from 0.0012 to 0.0043 µg/m
3
.