Industrial wastewater containing heavy metal Cr(VI) seriously affects the health of organisms and may even lead to cancer. Developing efficient adsorbents that can quickly separate heavy metals is crucial for treating wastewater. In this study, magnetic multiwalled carbon nanotubes (MMWCNTs) with moderate particle size and abundant surface active sites were prepared by coating multiwalled carbon nanotubes with magnetic nanoparticles. The results of FTIR, XRD, TG, VSM, BET, and EDS showed MWCNTs completely encapsulated on the surface of the magnetic nanoparticles, with a particle size of approximately 30 nm. Oxygenated groups provided abundant surface active sites and formed numerous mesopores. The response surface methodology was used to optimize the adsorbent dose, adsorption contact time and adsorption temperature, and the removal rate of Cr(VI) was more than 95%. The quasi-second order kinetics and Freundlich adsorption isotherm model explained the adsorption process to Cr(VI). MMWCNTs interacted with Cr(VI) through electrostatic attraction, reduction reactions, complexation, and other means. The extensive hydrogen bonding of the green solvent deep eutectic solvent (DES) was employed to desorb the MMWCNTs and desorption rate exceed 90%. Even after five adsorption-regeneration cycles, the adsorbent maintained a high capacity. In conclusion, these novel MMWCNTs, as efficient adsorbents paired with DES desorption, hold broad potential for application in the treatment of Cr(VI)-contaminated wastewater.