Radiation-induced graft polymerization of acrylic acid onto poly(tetrafluoroethylene-perfluorovinyl ether) copolymer films has been prepared using gamma-irradiation by the mutual method. The grafted copolymer rapidly complexes with rhodium ions through the carboxylic groups. The complexation process was followed by measuring the variation of the pH of aqueous RhCl3 solution of several concentrations as a function of time. Spectroscopic, electrical, optical, thermal, and diffraction measurements have been investigated. The results revealed the high stability of the ligand-metal complex formed. Thus, a practical application of the grafted copolymer in the field of rare metal waste treatment is implied.