Bifunctional fibers containing phosphonate and sulfonate were derived from chloromethylstyrene grafted polyolefin fibers (PPPE-g-CMS) by phosphorylation and subsequent sulfionation 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 AICl(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 sulfionation 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. (c) 2008 Elsevier Ltd. All rights reserved.