In this paper, a new rapid and sensitive method based on sodium dodecyl sulfate modified Fe۳O۴@α–Linolenic acid nanocomposite combined with high-performance liquid chromatography-photo diode array detection (HPLC–PDA) has been proposed for the extraction and determination of tramadol (TRA) in water samples. The Fe۳O۴@α–Linolenic acid NPs were synthesized and then characterized by Fourier transform-infrared spectroscopy (FT−IR), scanning electron microscopy (SEM) and X-ray diffraction (XRD). The main factors influencing extraction and desorption efficiency were optimized. Under optimum conditions, the method was successfully applied to the determination of TRA in the environmental samples and good linearity in the range of ۰.۱–۵۰۰ng.mL-۱(𝑅۲> ۰.۹۹) obtained. The detection limit (LOD) and relative standard deviation (RSD) were۰.۰۷۴ng.mL-۱ and ۲.۸۹ %( n=۵) respectively. Finally, the proposed method was successfully applied with the relative recoveries percentages from ۹۴–۱۰۳.۹۷% for the extraction and determination of tramadol in aqueous samples.