A kind of polyacrylonitrile (PAN) nanofibers which was reinforced with nylon (PA-66) fiber was fabricated via twin-spinneret electrospinning technology, then together with hydroxylamine hydrochloride produce oximation reaction to prepare the amidoxime modified polyacrylonitrile/nylon composite nanofibers (AOPAN/PA-66). The composition, morphology and mechanical properties of the nanofibers before and after oximation reaction were characterized by Fourier transform infrared spectroscopy and scanning electron microscope, and the adsorption properties were evaluated with Cu (II) and Pb (II). The results show that the compound fiber membrane have great mechanical properties with the tensile strength of 4. 73 MPa, elongation at break is 30. 76% and when the concentration of heavy metal ion is 500 mg/L, the highest adsorption capacity of AOPAN/PA-66 nanofiber membrane for Cu (II) and Pb (II) are 67. 5 and 75. 4 mg/g respectively.