A method for the qualitative analysis of various metabolites of naphthalene, phenanthrene and pyrene is presented. The method uses SPME with a 85-μm polyacrylate fibre for extraction, head-space silylation with BSTFA without any catalyst for on-fibre derivatisation and GC-MS in the SIR mode for separation and detection. The suitability of the method for profile analysis of PAH metabolites is shown by analysing a smokers urine after enzymatic cleavage (and additionally after spiking with the target analytes)-and spiked water. The method exhibits satisfactory separation of all investigated metabolites and no interferences due to matrix peaks.