Magnetic biochar composites (MBC) were developed by a simple one-step pyrolysis method using Fenton sludge waste solid and carboxymethyl cellulose sodium. Detailed morphological, chemical, and magnetic characterizations corroborate the successful fabrication of MBC. Batch adsorption experiments show that the synthesized MBC owns high-efficiency removal of Pb(II), accompanied by ease-of-separation from aqueous solution using magnetic field. The experiment shows that the equilibrium adsorption capacity of MBC for Pb(II) can reach 199.9 mg g−1, corresponding to a removal rate of 99.9%, and the maximum adsorption capacity (qm) reaches 570.7 mg g−1, which is significantly better than that of the recently reported magnetic similar materials. The adsorption of Pb(II) by MBC complies with the pseudo second-order equation and Langmuir isotherm model, and the adsorption is a spontaneous, endothermic chemical process. Investigations on the adsorption mechanism show that the combination of Pb(II) with the oxygen-containing functional groups (carboxyl, hydroxyl, etc.) on biochar with a higher specific surface area are the decisive factors. The merits of reusing solid waste resource, namely excellent selectivity, easy separation, and simple preparation make the MBC a promising candidate of Pb(II) purifier.