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Herein, the composite of polylactic acid (PLA)/ Iron-based metal-organic framework (r-MIL-88A)/ Cellulose electrospun nanofibers was fabricated; and then, applied as a novel sorbent for thin-film micro-extraction (TFME) of four selected pesticides followed by GC-FID analysis. From the evaluation of scanning electron microscopy, Fourier transform infrared spectroscopy energy dispersive X-ray spectroscopy and X-ray diffraction, the successful fabrication of composite nanaofibers was approved. The presence of r-MIL-88A/Cellulose with large surface area and plenty of OH-functional groups results in improving PLA extraction efficiency. The effect of various main parameters on extraction efficiency was evaluated. The LODs (based on S/N = 3) were in the range of 1.0 to 1.5 ng mL⁻¹. Intra-day and inter-day relative standard deviations (RSDs) were in the range of 4.8% - 5.6% and 5.2%-6.4%, respectively. In addition …