Abstract A method based on solid-phase microextraction (SPME) and gas chromatography with mass spectrometry (GC/MS) for the determination of 10 organochlorine pesticides (OCPs) in ecological textiles was described. Commercially available SPME fibers, 100 μm PDMS, 85 μm PA, 65 μm PDMS–DVB, 75 μm CAR/PDMS and 30 μm PDMS were compared and 100 μm PDMS exhibited the best performance to the OCPs. Various parameters affecting the extraction efficiency of SPME were optimized, including extraction time, desorption time, extraction temperature, salinity and pH. The optimized conditions were 40 min extraction at room temperature, 2% NaCl content, pH 6.0, and 4.0 min desorption in GC injector port at 250 °C. Under the optimized conditions, the limits of detections ranged from 0.04 μg L− 1 (dieldrin) to 0.41 μg L− 1 (aldrin) and the RSDs were between 3.2% and 11.3%. The optimized method was then used to analyze 10 OCPs in textile samples, and good relative recoveries were obtained (from 70.0 to 112.6%). This study illustrated the potential applicability of SPME for routine analysis of OCPs in textiles.