In this paper, electrospun Nylon6 nanofibrous membrane was firstly used as adsorbent for solid membrane extraction (SME). The membrane was arranged as a disk in a home-made device, three estrogens-estradiol (E2), ethinylestradiol (EE2) and estrone (E1) in environmental water were extracted and then determined by liquid chromatography-ultraviolet detector (LC-UV). The important parameters affecting extraction efficiency were completely studied and optimized. The experimental results showed that only 1.5 mg Nylon6 nanofibrous membrane could make the maximum sample loading volume up to 50 mL and the target analytes were adsorbed effectively. Under the optimized conditions, the limits of detection (LOD) for E2, EE2, E1 were up to 0.05, 0.08, 0.17 ng mL(-1) respectively and the repeatabilities (RSD%) of intra-membrane and inter-membrane were below 6.0% about spiked samples. The proposed method was subsequently applied to studying water samples from river, rain, pond and tap. Satisfactory spiked recoveries in the range of 85.3-95.9% at 0.25 ng mL(-1) spiked level for the three estrogens were obtained. A comparison with commercial nylon microporous membrane and octadecylsilica (ODS) cartridges was also carried out. All the results showed that electrospun Nylon6 nanofibrous membrane, as a new adsorbent material has great potential for the enrichment of steroid estrogens in the water samples with satisfactory recovery and repeatability.