Concern about the increasing atmospheric CO2 concentration and its impact on the environment has led to increasing attention directed toward finding advanced materials and technologies suited for efficient CO2 capture, storage and purification of clean-burning natural gas. In this letter, we have performed comprehensive theoretical investigation of CO2, N2, CH4 and H2 adsorption on B2CNTs. Our study shows that CO2 molecules can form strong interactions with B2CNTs with different charge states. However, N2, CH 4 and H2 can only form very weak interactions with B 2CNTs. Therefore, the study demonstrates B2CNTs could sever as promising materials for CO2 capture and gas separation. © 2013 Elsevier B.V. All rights reserved.