A cloud-point extraction (CPE) method using the surfactant (30)p-tert-octylphenol polyoxyethylene (OPEO30) was proposed as the preceding step for the determination of polycyclic aromatic hydrocarbons (PAHs) by gas chromatography-mass spectrometry (GC-MS). Given the need for surfactant derivatization before the chromatographic analysis, the reaction conditions of coacervate derivatization were studied. The extraction process was also optimized, where surfactant concentration, temperature and time were analyzed as variables. The limits of detection obtained were between 0.02 and 0.05 µg L-1, and the recoveries of analytes were between 70 and 98%, with coefficient of variation better than 10.3%. The analytical method developed provides an efficient, precise and accurate method for the determination of the 16 priority PAHs, generating results in accordance with the USEPA 3510C method. The method was applied to the analysis of groundwater samples collected from artesian wells located at retail fuel stations.