Nanofibers were novelly applied to the pretreatment of environmental estrogens in the water samples based on the adsorption ability due to their large surface areas. The method for extraction was validated, with the optimization of involved parameters such as nanofiber diameter, ionic strength of sample solution and pH value. Under optimized conditions, the good linearity of analytes was achieved in the range of 20～1000 ng/mL. The repeatability of extraction performance, which is expressed as relative standard deviations, was 3.97%～7.87%, corresponding to the water samples at 50～500 ng/mL spiked level for six kinds of compounds. The limits of detection (LODs) varied from 1.0 ng/mL to 2.5 ng/mL (S/N=3). The absolute recoveries were 57.9%～83.3%. The new method reduces the sample preparation time, the organic solvent consumption, and the damage to persons and environment, and improves the sensitivity and reproducibility for the investigated compounds. The present results indicate that the new method is a viable and environmentally friendly technique for analyzing environmental estrogens.