The present study was conducted to synthesize hybrid MOFs with a high effective surface area consisting of ZIF-8 and ZIF-90 on the surface of Graphene Oxide (GO). The hybrid ZIF-8-90@GO was finally placed inside the Hollow Fiber (HF) pores to use the substrate filtration properties. Then, the extraction device was used to extract three selected phthalate esters including DiMethyl Phthalate (DMP), DiEthyl Phthalate (DEP) and DiButyl Phthalate (DBP) (as the model analytes) followed by back extraction using Deep Eutectic Solvent (DES). Herein, the DES was utilized as a suitable and effective alternative to common toxic desorption solvents, and it led to the greening of the method. In order to achieve maximum efficiency and sensitivity, the parameters influencing on extraction and desorption processes were optimized. In the obtained optimum situation, the method linearity, Limits Of Detection (LODs), Limits Of Quantification (LOQs), Relative Standard Deviations (RSDs%), Enrichment Factors (EFs) were equal to 0.1–500 µg/L, 0.026–0.058 µg/L, 0.089–0.194 µg/L, 1.8 to 4.7% and 45.4–47.1, respectively. The obtained coefficients of determination (r2) were also higher than 0.9990. The Extraction Recovery (%ER) values were also 90, 87 and 91%, respectively for DMP, DEP and DBP. The above-mentioned method was used for the analysis of water and juice samples and acceptable results were obtained. The obtained relative recoveries in the real samples were in the range of 90–103%. Moreover, due to the presence of aldehyde and methyl groups with hydrophilic and hydrophobic properties in the structure of the synthesized hybrid sorbent, the possibility of interaction increased between sorbent and the studied species, and it per se, led to the increase of extraction efficiency.
