AbstractFor the first time, this research aims to develop a MIL‐53 (Fe)‐based dispersive micro solid‐phase extraction method prior to dispersive liquid‐liquid microextraction for the extraction and preconcentration of some pesticides and their analysis using a gas chromatography–flame ionization detector. For performing the extraction procedure, MIL‐53 (Fe) was added to an aqueous solution containing the analytes and vortexed to be dispersed in the solution and adsorb the analytes. After centrifugation, the analytes loaded on the adsorbent were eluted using acetonitrile. Then, μL‐level of carbon tetrachloride, as an extractant, was mixed with the obtained acetonitrile phase and injected into deionized water. One microliter of the sedimented phase after centrifugation was injected into the separation system. Satisfactory analytical results such as wide linear ranges, high enrichment factors (250–380), reasonable extraction recoveries (50–76%), and low limits of detection (0.63–2.05 μg L−1) and quantification (2.11–6.83 μg L−1) were obtained. Using only 5.0 mg MIL‐53 (Fe) as the sorbent, 0.5 mL acetonitrile as the elution/disperser solvent, and 40 μL carbon tetrachloride as the extractant makes the analytical approach so precious. Also, using a green metal, iron, as the central ion of the metal‐organic framework is another beneficial aspect of the research.