In this study, the bamboo biomass loaded with ethylenediaminetetraacetic acid (EDTA) intercalated Mg/Al-layered double hydroxides (LDH) was calcined to obtain a novel nano-adsorbent (BC@EDTA-LDH), and BC@EDTA-LDH was used to remove hexavalent chromium (Cr(VI)) in aqueous solutions. The results showed that the interaction between LDH and Cr(VI) on biochar played a dominant part in adsorption. The LDH of Cr(VI) intercalation was successfully reconstructed after adsorption. Fourier transform infrared spectra and X-ray diffraction results confirmed the reconstruction of Mg/Al-LDH. LDH had sustained release effect on the solution. As the pH values increased, the electrostatic repulsion between Cr2O72- and OH-increased, and there existed competition for adsorption sites. The maximum adsorption capacity of Cr(VI) was 38 mg/g. The data was well-fitted with pseudo second-order model and Langmuir-Freundlich model. BC@EDTA-LDH showed a high adsorption capacity and was potentially suitable for removing heavy metals in wastewater.