Reducing CO2 emissions is an urgent issueadsorption technologies based on solid adsorbents are considered a promising approach for CO2 capture. Pressure swing adsorption (PSA) shows potential to lower the environmental, energy,economic costs of CO2 separations. In this technology, a porous molecular crystal (PMC) assembled by close packing of macrocyclic organic molecules is used as an efficient adsorbent for CO2 capture. The eluted N2CH4 by PSA are obtained with over 99.999.8 purity, respectively.