The precursor polyacrylonitrile/poly(vinyl alcohol) (PAN/PVA) fibers were prepared by emulsion spinning of PAN emulsion with PVA solution. The precursor fibers were then amidoximated to get the polyamidoxime (PAO)/PVA composite chelating fibers. The structures of PAN emulsion particles and composite fiber were studied with a laser mastersizer, scan electronic microscope, Fourier transform infrared spectra, auto-Kjeldahl determination, and X-ray diffraction analysis. Results show that nanosized PAN particles were well-dispersed in PVA fiber matrix through emulsion spinning. Almost all of the PAN particles were amidoximated after treatment. The PAO/PVA fiber has good selectivity to silver ions in a multiple metal ions solution. Its maximum amount of adsorption of silver ions and copper ions were calculated to be 518 and 146 mg g(-1) according to the Langmuir model. It also has good mechanical performance with breaking strength, 392.10 MPa, and elongation at break, 30.19%.