Covalent cross-linked hydrogels based on chitosan and poly(maleic acid--vinyl acetate) were prepared as spherical beads. The structural modifications of the beads during the preparation steps (dropping in liquid nitrogen and lyophilization, thermal treatment, washing with water, and treatment with NaOH) were monitored by FT-IR spectroscopy. The hydrogel beads have a porous inner structure, as shown by SEM microscopy; moreover, they are stable in acidic and basic pH due to the covalent crosslinking. The swelling degree is strongly influenced by the pH since the beads possess ionizable amine and carboxylic groups. The binding capacity for Cu ions was examined in batch mode as a function of sorbent composition, pH, contact time, and the initial concentration of Cu. The kinetic data were well-fitted with the pseudo-second-order kinetic, while the sorption equilibrium data were better fitted with Langmuir and Sips isotherms. The maximum equilibrium sorption capacity was higher for the beads obtained with a 3:1 molar ratio between the maleic copolymer and chitosan (142.4 mg Cu g), compared with the beads obtained using a 1:1 molar ratio (103.7 mg Cu g). The beads show a high degree of reusability since no notable decrease in the sorption capacity was observed after five consecutive sorption/desorption cycles.