A novel kind of Levextrel resin with trialkylphosphine oxide (TRPO) extractant impregnated in the styrene-divinylbenzene copolymerization was synthesized. The extraction behavior of the resin toward Zr (IV) and Nd (III) ions was investigated by batch and column operations. The influence factors such as suspension system, porogen content, stirring rate, and temperature were systematically examined. The TRPO impregnated Levextrel resin showed excellent extraction ability toward the metal ions. The adsorption capacity of 47 mg/g for Zr (IV) ion and 48 mg/g for Nd (III) ion could be obtained in 1.0 g/L solutions. The fast kinetics in the extraction process was another noteworthy feature of the resin. The numerous micro- and macro-pores in the internal resin facilitated the mass transfer, and the equilibrium could be reached in only tens of minutes. Besides, the cyclic operations showed that the resin had a reliable performance and could be conveniently recovered. The TRPO impregnated Levextrel resin possesses the potential for the removal of the lanthanides and actinides ions in radioactive liquid waste.