In the present study, polystyrene nanofibers (PS NFs) were synthesized by electrospinning method and used as adsorbents in solid phase extraction of phenol from aqueous solutions. Phenol was reacted with 4-aminoantipyrine (4-AAP) reagent in presence of potassium hexacyanoferrate (III). The coloured product was extracted by solid phase extraction using electrospun synthesized polystyrene nanofibers and determined by UV-Vis spectrophotometer. At certain conditions of electrospinning process, the variables affecting the solid phase extraction efficiency were studied and optimized. Under the optimized conditions, (sorbent mass: 0.025 g PS NF, sample flow rate: 2.5 mL min−1, eluent: acetone: NaOH 0.1 M (1:1 v/v)), the linear dynamic range (LDR) and limit of detection (LOD as 3 Sb/m) for extraction of phenol from 50 mL of aqueous solutions were determined as 15-2500 µg L-1 and 10 µg L-1, respectively. The precision (as RSD %) of the extraction method using the proposed adsorbent was lower than 7.6%. Finally, the applicability of the proposed method for the extraction of phenol from industrial aqueous samples was examined and satisfactory results were obtained.