The recovery of precious metals, such as palladium (Pd), from wastewater, is an economically important field. The present study reports the application of polyglycidyl methacrylate (PGMA) macroporous spheres with diethylaminoethyl (DEAE) functional groups (PGMA−DEAE) for the adsorption of palladium ions [Pd(II)] from simulated wastewater solutions. The effects of pH, adsorption duration, and initial concentration of Pd(II) on the adsorption amount were evaluated systematically. The results revealed that within the experimental pH range, the adsorption efficiency of Pd(II) increased with increasing pH. In particular, between pH 4 and 6, the Pd(II) adsorption efficiencies were approximately 100%. At 298 K and pH ∼ 4, the adsorption capacity of PGMA−DEAE for Pd(II) was 1.22 mmol/g. The adsorption rates of PGMA−DEAE for Pd(II) were high, and the adsorption equilibrium was reached within 10 min. Ca(II), Mg(II), Co(II), Cu(II), Ni(II), and Fe(II) were selected as representative competitive adsorption metal ions. PGMA−DEAE had good separation selectivity for Pd(II) at pH 1−6 (all R Pd/Me > 30), especially at pH ∼ 4 (all R Pd/Me > 100). The SEM, TEM, EDS, TG, XRD, and XPS results indicated that in a high-acidity environment (C HCl ≥ 1 mol/L), Pd(II) was adsorbed on PGMA− DEAE through electrostatic attraction, while in a low-acidity environment (pH 1−6), Pd(II) was adsorbed on PGMA−DEAE through coordinated bonding between the Pd(II) ions and the N. PGMA−DEAE exhibited excellent stability and regeneration performance for five regeneration cycles.