A novel hollow fiber cation-exchange membrane was prepared from a bromomethylated poly(2,6-dimethyl-1,4-phenylene oxide) hollow fiber by amination and sulfonation. The membrane exhibited good performance for adsorption of Cu2+, and its maximum capacity can reach 69.12 mg/g. In particular, the adsorption capacity increased with an increase in adsorption time, initial Cu2+ concentration, and ion-exchange capacity of the membrane, and the adsorption isotherms were of Langmuir and Freundlich types. When these membranes were taken for desorption in solutions of hydrochloric acid, the regeneration ratio increased with an increase in regeneration time (before 20 min) and acid concentration. This study can provide new material for removal of heavy-metal ions in an energy-saving manner.