In this work, a porous multi-functional biomass carbon was prepared by acid-base modification method, which realized the reuse of waste cotton material. Then, the modified biochar was combined with the acrylic-based hydrogel by radical polymerization, and the biochar acrylic-based hydrogel (CS/EDTA/CBC) composite with chitosan and ethylenediamine tetraacetic acid was successfully prepared. This not only increases the adsorption performance of the adsorbent but also improves the stability of hydrogel. These characteristics provide high-efficiency adsorption capacity for pollutants (1105.78 mg g−1 for Pb2+, 678.04 mg g−1 for Cu2+, and 590.72 mg g−1 for methylene blue (MB)), which is far superior to most reported adsorbents. Meanwhile, the adsorbent would have a strong chemical interaction with Pb2+ and Cu2+, can form a stable chelating structure, and showed stronger selective adsorption. The adsorption process is more suitable for the Langmuir isotherm and follows a pseudo-second-order kinetic model, which indicates that the adsorption is a single-layer adsorption, and the rate-limiting step is a chemical chelation reaction. XPS results confirmed that surface complexation and electrostatic attraction are the main mechanisms of the adsorption reaction. After five cycles, the adsorption capacity of the adsorbent and the recovery of heavy metal ions remained at a high level.