A magnetic cotton stalk biochar (MCSBC) was synthesized through chemical co-precipitation, based on cotton stalk biochar (CSBC). The MCSBC and CSBC were characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy and vibrating sample magnetometry. The characterization analyses showed that the magnetization process endowed the CSBC with excellent magnetic properties with a superparamagnetic magnetization of 27.59 emu/g. Batch adsorption experiment results indicated that the Cr(VI) maximum adsorption capacity of MCSBC was 20.05 mg/g, which was higher than that of CSBC (18.77 mg/g). The adsorption kinetic data were well fitted by the pseudo-second-order model and the adsorption isotherms were well represented by the Sips isotherm model. The thermodynamic studies indicated that the adsorption process was spontaneous and endothermic, and the entropy increased. The potential adsorption mechanism was the electrostatic adsorption of anionic Cr(VI) to the positively charged MCSBC surface, the reduction of Cr(VI) into Cr(III) and the complexation of Cr(III) by oxygen-containing functional groups of MCSBC. The regeneration studies showed that MCSBC kept 80% of its initial Cr(VI) adsorption capacity in the cycle. All the findings suggest that this novel magnetic biochar could be used in the field of Cr(VI)-containing wastewater treatment.