In order to have an efficient adsorptive separation, structured adsorbents are expected to satisfy not only mass transfer and pressure drop requirements but also thermal management requirements. To what extent the structure of adsorbent affects the thermal behavior of the system is a question which will be addressed in this study. The primary purpose of this study was to assess the performance of alternate adsorbents through development of numerical models for prediction of their thermal behavior under a two-step pressure swing adsorption (PSA) condition. The single-step CO2 breakthrough and temperature profiles confirmed the efficiency of structured adsorbents in managing the thermal effects evolved in the bed under nonisothermal conditions. Two-step PSA results also showed that under real cyclic processes, and especially during rapid cycling, structured adsorbents maintain their superiority and introduce themselves as potential candidates for advanced PSA units. However, the performance of a structured adsorbent is highly dependent on its dimensions and geometrical parameters describing the structures, and these parameters should be optimized for each separation.