A sensitive method for the extraction and determination of polycyclic aromatic hydrocarbons (PAHs) using alcoholic-assisted dispersive liquid–liquid microextraction (AADLLME) and HPLC was developed. The extraction procedure was based on alcoholic solvents for both extraction and dispersive solvents. The effective parameters (type and volume of extraction and dispersive solvents, amount of salt and stirring time) on the extraction recovery were studied and optimized utilizing factorial design (FD) and central composite design (CCD). The best recovery was achieved by FD using 2-ethyl-1-hexanol as the extraction solvent and methanol as the dispersive solvent. The results showed that volume of dispersive solvent and stirring time had no effect on the recovery of PAHs. The optimized conditions were 145 mL of 2-ethyl-1-hexanol as the extraction solvent and 4.2% w/v of salt (NaCl) in sample solution. The enrichment factors of PAHs were in the range of 310–325 with limits of detection of 0.002–0.8 ng/mL. The linearity was 0.01–800 ng/mL for different PAHs. The relative standard deviation (RSD) for intra- and inter-day of extraction of PAHs were in the range of 1.7–7.0 and 5.6–7.3, respectively, for five measurements. The method was also successfully applied for the determination of PAHs in environmental water samples.
