Highly ordered porous materials having mesopores in the walls of macropores showed improved adsorption dynamics results for VOC molecules, especially bulky molecules. These meso/macroporous mataerials were synthesized by the dual templating method, and mesopore and macropore size were controlled by adjusting the templates for each pore size regime. In the case of adsorption and desorption of small VOC molecules (toluene), although meso/macroporous MCM-41 with smaller mesopore size showed improved results, meso/macroporous SBA-15 with larger mesopore size was not improved regardless of the existence of macropores, since there was no limitation of movement through the larger mesopore. However, the adsorption dynamics of bulky VOC molecules (p-xylene) over meso/macroporous SBA-15 were drastically improved by increasing the macropore size.