In this research nanostructural poly (o-aminophenol) was synthesized by electropolymerization and used for solid phase microextraction procedure (SPME). Thin film of Poly (o-aminophenol) (4 µm thickness) was shaped by sweep potential for 45 min on the surface of stainless steel wire. Polymer was synthesized by potentiostat procedure too. Prepared polymer by sweep potential procedure showed nanostructures on the surface. Acetic anhydride was employed for derivatization of bisphenol A (BPh-A) and analysis of acetylated BPh-A was utilized by gas chromatography-flame ionization detector (GC-FID). Affecting parameters on derivatization and extraction such as amount of acetic anhydride, stirring rate, temperature, ionic strength and extraction time were optimized. The limit of detection (LOD) and relative standard divisions (RSDs%) were achieved 0.6 µgL-1 and less than 6.8%, respectively under optimized conditions. Finally proposed method was used for extraction of bisphenol A from leaching of baby and drinking water bottles. Relative recovery was achieved 98% for leaching from drinking bottle. In leaching from plastic baby bottle, bisphenol A (BPh-A) was detected in the range 5–15 µg L-1.