In this research, 16 polycyclic aromatic hydrocarbons (PAHs) in bread samples were simultaneously determined using microwave-assisted extraction and dispersive liquid–liquid microextraction (MAE– DLLME) coupled with gas chromatography-mass spectrometry (GC-MS). Effective parameters of MAE– DLLME were investigated and optimized using a response surface methodology based on central composite design (CCD). Under optimum conditions, linearity was obtained in the range of 1–200 ng g1 for 16 PAHs, with a correlation coefficient (R2) better than 0.9833. The limits of detection and limits of quantitation for PAHs in real samples were over the ranges 0.1 to 0.3 ng g1 and 0.3–1 ng g1, respectively. The performance of the proposed method was investigated for the determination of PAHs in various bread samples and acceptable results were obtained.