Gas adsorption studies (CO2 and N2) over a wide pressure range on vertically, highly aligned dense double-walled carbon nanotube arrays of high purity and high specific surface area are reported. At high pressures, the adsorption capacity of these materials was found to be comparable to those of metal organic frameworks and mesoporous molecular sieves. These highly aligned CNT arrays were chemically modified by treating with oxygen plasma and structurally modified by decreasing the diameter of individual carbon nanotubes. Oxygen plasma treatment led to grafting of a large number of C-O functional groups onto the CNT surface, which further increased the gas adsorption capacity. It was found that gas adsorption is dependent on tube diameter and increases with decrease of the individual CNT diameter in the CNT bundles. As results of our studies we have found that at lower pressure regimes, plasma functionalized carbon nanotubes exhibit better adsorption characteristics whereas at higher pressures, lower diameter carbon nanotube structures exhibited better gas adsorption characteristics. © 2013 Elsevier Ltd. All rights reserved.