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A new type of biochar, called GBC, was prepared from silkworm excrement, and then modified by chitosan combined with pyromellitic dianhydride. The removal of mono-metal and polymetals (Pb, Cd and Cu) from an aqueous solution by GBC was investigated in this research. Compared to unmodified biochar, the removal rate of Pb and Cd by GBC was about 12% higher, while that of Cu was about 94.6% higher. It also shows the types of functional groups in biochar have a great impact on their adsorption. The removal of Pb is mainly involved in the N-C=O functional group, the removal of Cd is mainly involved in N-containing functional group and C=C bond, and that of Cu is mainly involved in N-containing functional group, carboxyl group, hydroxyl group, and a carbonyl group. Five adsorption–desorption cycles of GBC were carried out, and it was found that the adsorption capacities of GBC for Pb, Cd and Cu decreased by 7.28%, 10.78% and 6.07%, respectively, indicating that GBC had a good renewable performance. The adsorption capacity of GBC for Cu in different water samples is between 89.62 and 93.47 mg·g⁻¹, indicating that GBC has great application potential for the removal of Cu in wastewater.