Residual diclofenac sodium (DS) in water is a potential hazard. The electrostatic attraction between amino group of adsorbents and carboxyl group of DS under acidic conditions can effectively remove DS from water. Herein, a novel core–shell adsorbent of poly(vinyl alcohol)/chitosan/amino-grafted silica@polyethylenimine (PVA/CS/SAP@PEI) gel bead was prepared to efficiently uptake DS from wastewater. In this study, the gel bead was characterized using FTIR, XPS, SEM, EDS, and 13 C NMR. The experimental data shows that there is a strong correlation between adsorption capacity. The adsorption data fitted well with the Freundlich isotherm model and the pseudo-second-order model. The results of thermodynamics show that the adsorption process is spontaneous, endothermic, and increases entropy. The maximum adsorption capacity for DS was calculated as 493.81 mg/g at pH 5 (308 K). The adsorbent still exhibited excellent adsorption capacity after recycling five times, showing it has excellent potential for practical applications.