A new type of adsorbent containing amidoxime and carboxyl groups was synthesized by the preirradiation graft copolymerization of acrylonitrile (AN) and acrylic acid (AA) onto fibrous-type poly(vinyl alcohol) followed by amidoximation with hydroxylamine. The radiation dose and ratio of AN and AA monomers influenced the degree of grafting, the content of the amidoxime group, and the adsorption capacity. The synthesis course, structure, and properties of the adsorbent were investigated with Fourier transform infrared, scanning electron microscopy, and thermogravimetry. The adsorption property of the adsorbent for palladium(II) ions was also studied systematically.