Cr(VI) is toxic to the organic life. Eliminating the pollutant of Cr(VI) in solution has become a hot research field. In this work, the C@K₂Ti₆O₁₃ hierarchical nanomaterials were prepared by liquid phase deposition combined with hydrothermal treatment, which were constituted by carbon nano spheres and K₂Ti₆O₁₃ nanobelts. The morphology and phase of the materials were characterized by different methods. The C@K₂Ti₆O₁₃ hierarchical nanomaterials show high potential as adsorbent to adsorb Cr(VI). Effect of initial pH, adsorption time and ionic strength on Cr(VI) adsorption by C@K₂Ti₆O₁₃ composite nanostructures were investigated. The elimination rate of Cr(VI) can reach 50% in 1 h. The adsorption kinetics agrees well with the pseudo- second-order kinetic model, and the adsorption thermodynamics accords with the Langmuir isotherm adsorption model. It can be expected that the C@K₂Ti₆O₁₃ hierarchical nanomaterials have great application potential in environmental treatment.