Solid phase extraction (SPE) procedure followed by high‐performance liquid chromatography with fluorescence detection was evaluated for determination of 14 priority polycyclic aromatic hydrocarbons (PAHs) pollutants in water samples. Diverse parameters affecting extraction efficiency such as the nature and volume of eluent solvent, volume and pH of the water sample, and quantity and nature of sorbent phase were studied and optimized. SPE was carried out on Bond Elut C18 cartridge and high recoveries were obtained using 1000 mg of the sorbent for the treatment of a 500 mL water sample. PAH recoveries ranged from 60.3% to 93.3% for 500 mL treated water samples. The developed method gives very low detection limits ranging between 0.03 and 12 ng/mL and it has been applied successfully to different environmental water samples such as tap water, mineral water, surface water, treated wastewater, and industrial effluents. Results showed the presence of PAHs especially in industrial effluent from the Bizerte region with ∑PAHs means value of 33.76 mg/L and in treated wastewater samples collected from North Tunisia with ∑PAHs concentrations levels of 0.81, 1.17, 0.97, and 0.72 mg/L in Bizerte, Tunis, Ben Arous, and Beja wastewater treatment plants, respectively.