The use of porous materials in industrially important gas separation and purification applications, e.g. CO2 separation from flue gas and purification of biogas require that the porous material is assembled into mechanically strong and hierarchically porous macroscopic structures. Hierarchically porous structured monoliths[1-2] and laminates[3] have been reported with high performance for CO2 separation from N2. Such structured monoliths and laminates with tailored porosity at various length scales combined high volumetric efficiency, good mass and heat transfer, rapid adsorption/desorption kinetics and structural integrity[1-3]. Here, we demonstrate a binder-less approach[4,5] to consolidate 8-ring window zeolite and aluminophosphate (AlPO4’s) powders into mechanically strong monoliths with a high CO2 uptake capacity and CO2-over-N2 selectivity, and a rapid adsorption and release kinetics. Adsorption isotherms of CO2 and N2 were used to predict the co-adsorption of CO2 and N2 using ideal adsorbed solution theory (IAST). The IAST predictions showed that monolithic zeolite adsorbents of partially K exchanged NaA could reach an extraordinarily high CO2-over-N2 selectivity in a binary mixture with a composition similar to flue gas[1]. Furthermore, zeolite monoliths showed high tensile strength of 2.2 MPa. AlPO-17 and AlPO-53 monoliths were consolidated by the binder-less process with a tensile strength over 1 MPa. AlPO-17 monoliths showed high CO2 adsorption capacity while AlPO-53 exhibited high CO2-over-N2 selectivity. Cyclic CO2 adsorption tests showed that AlPO4 monoliths required less energy for regeneration compared to zeolite and could be regenerated to their full capacity at low pressures