In this study, a novel polystyrene-poly(hydroxamic acid) copolymer was synthesized as an effective adsorbent for the treatment of rare earth elements. Through the use of elemental analysis as well as FTIR, SEM, XPS, and Brunauer-Emmett-Teller (BET) surface area measurement, the synthesized polymer was found to have a specific surface area of 111.4 m2·g−1. The adsorption performances of rare metal ions were investigated under different pH levels, contact times, initial concentrations of rare earth ions, and temperatures. The adsorption equilibrium for La3+, Ce3+, and Y3+ onto a polystyrene-poly(hydroxamic acid) copolymer is described by the Langmuir model, which confirms the applicability of monolayer coverage of rare earth ions onto a polystyrene-poly(hydroxamic acid) copolymer. The amount of adsorption capacities for La3+, Ce3+, and Y3+ reached 1.27, 1.53, and 1.83 mmol·g−1 within four hours, respectively. The adsorption process was controlled by liquid film diffusion, particle diffusion, and chemical reaction simultaneously. The thermodynamic parameters, including the change of Gibbs free energy (∆G), the change of enthalpy (∆H), and the change of entropy (∆S), were determined. The results indicate that the adsorption of resins for La3+, Ce3+ and Y3+ was spontaneous and endothermic. The polymer was also used as a recyclable adsorbent by the desorption experiment.