Priority pollutants chlorophenols are broadly used chemicals that are persistent in the environment and causing serious human health hazards. The current study introduces a novel adsorbent for the extraction of chlorophenols from river water, surface water, and milk by headspace solid-phase microextraction coupled with gas chromatography. The adsorbent composite was prepared by blending polycaprolactam (nylon-6) mat and newly synthesized carbon nanotubes decorated with cadmium oxide nanoparticles followed by electrospinning technique to produce based nanofiber. The proposed nanofiber was characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, and X-ray diffraction techniques. The main parameters that affect extraction efficiency, including ionic strength, extraction time, desorption time, and extraction temperature, were investigated and optimized. The linear range was 0.05-5 ng/mL; the limits of detection (signal/noise=3) were 0.02-0.04 ng/mL. The relative recoveries for real samples (river water, surface water, and milk) were in the range of 84-114%.