Oxygenated PAHs (oxy-PAHs), such as hydroxylated PAHs (OHPAHs), PAH quinones (PAHQs) and carbonyl PAHs (oxo-PAHs), have been found in the atmosphere as well as in soot from automobile, soil, sediment, seawater and waste water. Gas chromatography with mass spectrometry (GC–MS) was preferred in the analysis of oxy-PAHs in the environmental samples and almost methods need acetyl derivatization to improve sensitivity. On the other hand, an advantage of LC-bases techniques is their good sensitivity without derivatization. The metabolites of PAHs and their derivatives in biological fluids have been investigated as potential biomarkers for assessing human exposure to them, and, particularly, urinary 1-hydroxypyrene and other OHPAHs have been used in various studies. Urinary OHPAHs have been frequently analyzed by HPLC with fluorescence detection and LC–MS/MS. The urinary metabolites of PAHQs (9,10-Phenanthrenequinone) and nitro-PAHs (1-nitropyrene) were identified by LC–MS/MS and suggested as a new type of biomarker.