Novel nanomaterials are promising for capture, storage and separation of CO2. By density functional calculations, we find that the newly discovered B-40 fullerene is a suitable candidate. CO2 forms stable chemisorptions with B-40 on specific sites, which is validated by the high adsorption energy, large charge transfer, and kinetic feasibility for B-40(CO2) complexes. Due to the strong chemisorption, B4(0) shows high adsorption capacity for CO2 (up to 13.87 mmol/g). In addition, B-40 shows good selectivity for CO2 and is efficient in separating it from gas mixtures like CO2/N-2, CO2/H-2, and CO2/CH4. (C) 2015 Elsevier B.V. All rights reserved.