In this method, a sorbent was made from non-toxic, environmentally friendly and inexpensive natural polymers. Electrospinning technique was used to fabricate the sorbent substrate. Natural cellulose acetate nanofiber was produced on a brass rod (stir bar) as the substrate. Then the substrate was dipped in the chitosan solution (as sorbent). After solvent evaporation, the dried stir bar immersed in gluteraldehyde solution until cross linking performed between polymeric chains. The prepared sorbent was used for the extraction of bisphenol A in aqueous solutions. In order to obtain the highest extraction yield, synthesis and extraction conditions was optimized. Best cellulose acetate nonofibers were achieved with 12% w/w cellulose acetate solution, feed rate 1mL/h, at 20 cm distance and 25 kV voltage. Extraction time of 30 minutes in 20 mL bisphenol A solution containing 0.3 g/mL sodium sulfate and desorption time of 20 minutes using 750µL methanol solvent, was chosen as the best extraction conditions. High performance liquid chromatography with ultraviolet detector was used for the sake of chromatographic analysis. The detection limit and dynamic range of the method were 0.1 µg/L and 0.3-100 µg/L, respectively. Relative standard deviation was in the range of 1.5-6.4% . Finally three real samples obtained from baby bottle, Isfahan Zayande Rood river and well water were used in order to evaluate the method. After spiking the real samples in two concentration levels (10 and 50 µg/L), relative recoveries and RSDs were obtained in the range of 95-112 % and 0.9-7.9 %, respectively.