The present study explains the in situ growth of Cu cluster-based metalorganic framework on copper substrate for thin film microextraction approach. Cu cluster-based metal-organic framework has been growth via a hydrothermal method on electrochemically anodized copper substrate. After thin film microextraction, some polycyclic aromatic hydrocarbons were quantified via high performance liquid chromatography- photo diode array detection. The influence of effective parameters such as extraction time, extraction temperature, agitator speed and ionic strength of the sample was investigated and the optimum conditions were chosen. Calibration curves were obtained in 0.0001–10 mgL1 range with acceptable linearity as R2 > 0.986. The range of 1 and 3 pgL1 was calculated as limits of detection, with the relative standard division below 5.1% in the optimal condition. For evaluating the model, samples from river water and wastewater were used and investigated. It was found that relative recoveries were between 96-104%. The proposed method provided a simple, efficient and environmental approach for the rapid and convenient determination of polycyclic aromatic hydrocarbons in real samples.