Polyacrylonitrile (PAN) nanofibers were applied to metal adsorption. PAN nanofibers (prepared by an electrospinning technique) were chemically modified with amidoxime groups, which are suitable for metal adsorption due to their high adsorption affinity for metal ions. The adsorption of the amidoxime-modified PAN (PAN-oxime) (25% conversion) nanofibers followed Langmuir isotherm. The saturation adsorption capacities for Cu(II) and Pb(II) of 52.70 and 263.45 mg/g (0.83 and 1.27 mmol/g), respectively, indicating that the monolayer adsorption occurred on the nanofiber mats. In addition, over 90% of metals were recovered from the metal-loaded PAN-oxime nanofibers in a 1 mol/L HNO3 solution after 1 h.