A simple, sensitive and selective method for extraction of trace amounts of Vanadium (V) in water samples based on the adsorption of its modification nano polyacrylonitrile fiber (PANF). PANF was prepared by adding acrylic fibers to Calix[4]resorcinarene-Hydroxamic Acidwith different concentration solutions. A new technique using a solid phase extraction (SPE) cartridge with modified nano polyacrylonitrile fiber as sorbent was developed for the preconcentration of trace amounts of Vanadium and was determined by flame atomic absorption spectrometry (FAAS). Ethylenediamine play a key role as chelating reagent on ultrahigh specific surface of PANF. Some of the important parameters on the preconcentration and complex formation were selected and optimized. Under the optimized conditions the limit of detection (LOD) and limit of quantification (LOQ) were 0.167,0.562 and the proposed method has a good reproducibility 0.81% (RSD %).The enrichment factor was 200 and the percentage of recovery was in the range of 95-100%. The method was successfully applied to the recovery of Vanadium(V) in different type of water samples. PANF and its derivate such as  PANF-CALIX[4]RESORCINARENE-HYDROXAMIC ACID (OFCHA) in this study is full of potential to use as an excellent adsorbent in the extraction method like solid phase extraction (SPE) and solid phase micro extraction (SPME).