A new HRGC–HRMS method was developed for determination of 4 OH-PAHs.
The causes of OH-PAHs instability were identified as photo induced oxidation.
The current method controlled OH-PAH analyte degradation during analysis.
Conjugated OH-PAHs are more stable than non-conjugated OH-PAHs.
Accuracy and precision were 77.4–117% (<15% RSD) in synthetic and human urine samples.