Bifunctional fibers containing phosphonate and sulfonate were derived from chloromethylstyrene grafted polyolefin fibers (PPPE-g-CMS) by phosphorylation and subsequent sulfonation reactions. It was clarified that phosphorylation of PPPE-g-CMS by Arbusov reaction is more suitable than one by the reaction with PCl 3 in the presence of AlCl 3 , because the latter damaged fibers and gave phosphinate groups in addition to phosphonate ones. Then, bifunctional fibers containing phosphonate and sulfonate groups were prepared by sulfonation of monofunctional phosphonate fibers obtained via Arbusov reaction with chlorosulfonic acid. The metal ion selectivity of the bifunctional fibers was governed by both phosphonate and sulfonate groups. In addition, bifunctional fibers gave much more excellent kinetic performances in column-mode uptake of Cu(II) than the monofunctional phosphonate fibers and resin.