Electrospun nanofibers from poly(methylmethacrylate) (PMMA) and polystyrene (PS) blend were used as a sorbent to extract tramadol from urine and plasma samples. Then, the tramadol concentration was determined by corona discharge ion mobility spectrometry. The hydrophilic (PMMA) and hydrophobic (PS) properties of the blend polymer improved extraction efficiency of the analyte. The scanning electron microscopy images of the PMMA/PS nanofibers showed a diameter range of 130-600 nm with a smooth morphology. Parameters affecting extraction efficiency were optimized and under the optimized conditions, the dynamic ranges and detection limit of tramadol were found to be 30-500 and 10-200 ng mL(-1), and 9.4 and 1.6 ng mL(-1) in plasma and urine samples, respectively.